CA1041101A - Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereof - Google Patents
Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereofInfo
- Publication number
- CA1041101A CA1041101A CA213,664A CA213664A CA1041101A CA 1041101 A CA1041101 A CA 1041101A CA 213664 A CA213664 A CA 213664A CA 1041101 A CA1041101 A CA 1041101A
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- percent
- radical
- weight
- carbon atoms
- ethylenically unsaturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/62—Y being a nitrogen atom, e.g. biuret
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
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- Chemical & Material Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Ethylenically unsaturated blocked aromatic diiso-cyanates are prepared which readily polymerized to form homo-polymers and interpolymers with copolymerizable vinylidene monomers. Polymers can be prepared via emulsion polymerization, and exhibit excellent stability to hydrolysis when stored in latex form. The polymers cure at temperatures as low as 80°C., and under acidic, neutral, or basic pH conditions. Homopolymers and interpolymers of the defined diisocyanates are useful as adhesives, and interpolymers of the ethylenically unsaturated blocked aromatic diisocyanates with acrylate monomers are particularly useful as binders for nonwoven fibers.
Ethylenically unsaturated blocked aromatic diiso-cyanates are prepared which readily polymerized to form homo-polymers and interpolymers with copolymerizable vinylidene monomers. Polymers can be prepared via emulsion polymerization, and exhibit excellent stability to hydrolysis when stored in latex form. The polymers cure at temperatures as low as 80°C., and under acidic, neutral, or basic pH conditions. Homopolymers and interpolymers of the defined diisocyanates are useful as adhesives, and interpolymers of the ethylenically unsaturated blocked aromatic diisocyanates with acrylate monomers are particularly useful as binders for nonwoven fibers.
Description
~ 04:~Q~
BACKGROUND OF THE INVENTION
Prior art disclosing polymerizable blocked isocyan-ates is as follows: U.S. Patent Nos. 2,483,194, 2,556,437,
BACKGROUND OF THE INVENTION
Prior art disclosing polymerizable blocked isocyan-ates is as follows: U.S. Patent Nos. 2,483,194, 2,556,437,
2,882,260; 3,261,817; 3,299,oo7; 3,542,739 and 3,694,146, and British Patent 1,288,225. Other relevant art is disclosed in -U.S. Patent Nos. 3,519,478, 3,694,389 and 3,711,571.
The novel ethylenically unsaturated blocked aromatic diisocyanates can be distinguished from other known polymeriz-able isocyanates by their ease of polymerization and copolymer-ization with vinylidene monomers, particularly in emulsion polymerization systems. The prepared polymers are quite stable to hydrolysis and can be stored in latex iorm.
Interpolymers o~ the novel diisocyanates with acrylate monomers have particular utility as binders for non-woven fibers such as paper, cotton, synthetic ~ibers, and the like. The fibers are coated or impregnated with the interpolymers which :
can then be cured at temperatures as low as 80C. and under acldlc, neutral, or basic pH conditions. This is in contrast ~;~
.
to the known acrylic or nitrile latex binders which require ~20 highly acidic (pH o~ about 2) conditlons to exhibit a strong fast cure at low temperatures. The hlghly acidic environment is undesirable a~ it can degrade some fibers, especially ; cellulose-type fibers, it can interfere with e~forts to thlcken the latex ~or more convenient use, and it can cause corrosion S~ARY OF THE INVENTION
Ethylenically unsaturated blocked aromatic diiso-cyanates are prepared having the formula R O O
", " ., ' :.'' ~ ~where~R~is hydrogen or a methyl or ethyl radical, A is a o~ .
carbonyloxyalkylene radical containing 2 to about 8 carbon atoms ~ -~or an aralkylene radical, B is a bivalent aromatic radical selected from the group consisting of arylene, napt~alene and the s~ructure R ~
n n where Y is O, S or--~CH2~ , where n = O to 3, and X is the radical fragment remaining by the removal of a hydrogen atom from the nitrogen atom of an oxime selected from the group consisting of acetoxime, methylethyl ketoxime, methylpropyl -ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclo-hexanone oxime, benzophenone oxime, benzoaldoxime; benzimi-dazole, a pyrazole, a pyrazole selected from the group consist-ing of pyrazole,3-methyl pyrazole, 3,5-dimethyl pyrazone; and a benzotriazole selected from the group consisting of benzo-triazole, 5-methylbenzotriazole, 6-ethylbenzotriazole, 5-chlorobenzotriazole and 5-nitrobenzotriazole.
The defined diisocyanates are readily polymerized, especially via emulsion polymerization techni~ues, to form polymers of from about 0.1 percent to 100 percent by weight (i.e., homopolymers) of the diisocyanate and up to 99~9 . .
percent by weight of a copolymerizable vinylidene monomer.
DETAILED DESCRIPTION OF THE INVENTIO~
The ethylenically unsaturated blocked aromatic di-isocyanates have the formula R O O
11 11 ' CH2=C-A-OC-N~I-B-NH-C-X . ~: ' wherein R is hydrogen or a methyl or ethyl radical, A is either -a carbonyoxyalkylene radical containing 2 to about 8 carbon atom,s or an aralkylene radical containing 7 to about 12 carbon atoms, ~ -3-,.
. :
B is a bivalent aromatic radical selected from the group consist-ing of arylene, napthalene, and the structure . . .
~~Y~O~
R'n n : ~ , . ., ., ~ . .
:' ' ' ' , . ' .,, '.
" ':
'.'; ~' ' ''' ' ' ~ ' " ~::: .
' :
-3a- .
1C34~
where R is defined as above~ Y is 0, S, or -~-CH2-~-n , n = O
to 3, and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime,benzimi~ole, pyrazole, benzotriazole, caprolactam, thiocaprolactam, or p-nitroaniline. The aromatic rings in A and/or B can be furthersubstituted with 1 to 4 carbon atom alkyl radicals. More preferredly, R is hydrogen or a methyl radical, B is selected from the group consisting of phenylene, tolylene, naphthalene, and the defined structure where Y is ~ CH2-~-n group and n = O to 1.
Examples of the unsaturated blocked aromatic diiso-cyanates are:
When ~rAI~ is a carbonyloxyalkylene radical:
O ' H O O NH-CO-N=C/ 3 ~ t~
CH2-C-CO-(CH2)2-OC-NH ~ CH3 C2H5 .
. CH2=C-CO-(CH2)3-OC-NH ~ NH-cO-N=c~c H
O
CH3 O O NH_co_N=c~ 2 5 CH2=C--CO- (CH2)2-OC-NH~CH3 C6H13 ~ ' , :
H O O O
CH2=C- CO- ( CH2 ) 4-OC-NH~II- C-N~
..~ .
_ 4 _ - . . - . . - . - .
, . . -10~
CH2=C - CO-(CH2)6-OC-NH ~ NH-CO-N-C~ 3 H O O O
CH2=C-CO-(CH2)-0C-NH-C2H4 ~ C2H4-NH-CO-N-C~ 3 ,CH3 ~t ~ <C2H5 CH2=C- CO-(CH2)3-0C-NH ~ . :
NH-C-N ~ ~ ~
' ' ' ' . ' : , , , C,2H5 ,0, ,ol CH3 CH3 ~N ~ CH3 CH2=C- C-(CH2)4-C-NH ~ CH2 ~ H C N ~ : , . :
::, ,.
H O O O . :
~ CH2-C-CO-(CH2)2-0C-NH ~ CH2-NH-C-NH ~ N02 ~ .
.:
O
H O O ~NH-CO-N=C~ 3 -CO-(CH2)4_0C_NH ~ Cl 3 7 ~.
C,H3 ,,~ i ~ 3 ~~ ~
CH2~C - C-(CH2)2-C-NH ~ b H3 < O ~ C2H5 -`.:. :: ' 104i~
O O CH O ~N
, 3 " " ~ 3 CH2=C C0-'CH2'5-OC-NH ~ CH-NH-C-N
O ~
~ ' ,N- N
CH O O NH-C-N~
~ 3 t~ t~
CH2=C CO-(CH2)2-Oc-NH ~ 3 ~ H
CH
H O O ~H-CO-N=C
CH2SC-CO-(CH2)2-OC-NH ~ CH3 2 5 O : ,:
" CH
CH3 O O NH-CO-N=C
CH2=C CO-(CH2)2-OC-NH ~ CH3 C4Hg .
, . ~' CH O O NH-C-N _
The novel ethylenically unsaturated blocked aromatic diisocyanates can be distinguished from other known polymeriz-able isocyanates by their ease of polymerization and copolymer-ization with vinylidene monomers, particularly in emulsion polymerization systems. The prepared polymers are quite stable to hydrolysis and can be stored in latex iorm.
Interpolymers o~ the novel diisocyanates with acrylate monomers have particular utility as binders for non-woven fibers such as paper, cotton, synthetic ~ibers, and the like. The fibers are coated or impregnated with the interpolymers which :
can then be cured at temperatures as low as 80C. and under acldlc, neutral, or basic pH conditions. This is in contrast ~;~
.
to the known acrylic or nitrile latex binders which require ~20 highly acidic (pH o~ about 2) conditlons to exhibit a strong fast cure at low temperatures. The hlghly acidic environment is undesirable a~ it can degrade some fibers, especially ; cellulose-type fibers, it can interfere with e~forts to thlcken the latex ~or more convenient use, and it can cause corrosion S~ARY OF THE INVENTION
Ethylenically unsaturated blocked aromatic diiso-cyanates are prepared having the formula R O O
", " ., ' :.'' ~ ~where~R~is hydrogen or a methyl or ethyl radical, A is a o~ .
carbonyloxyalkylene radical containing 2 to about 8 carbon atoms ~ -~or an aralkylene radical, B is a bivalent aromatic radical selected from the group consisting of arylene, napt~alene and the s~ructure R ~
n n where Y is O, S or--~CH2~ , where n = O to 3, and X is the radical fragment remaining by the removal of a hydrogen atom from the nitrogen atom of an oxime selected from the group consisting of acetoxime, methylethyl ketoxime, methylpropyl -ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclo-hexanone oxime, benzophenone oxime, benzoaldoxime; benzimi-dazole, a pyrazole, a pyrazole selected from the group consist-ing of pyrazole,3-methyl pyrazole, 3,5-dimethyl pyrazone; and a benzotriazole selected from the group consisting of benzo-triazole, 5-methylbenzotriazole, 6-ethylbenzotriazole, 5-chlorobenzotriazole and 5-nitrobenzotriazole.
The defined diisocyanates are readily polymerized, especially via emulsion polymerization techni~ues, to form polymers of from about 0.1 percent to 100 percent by weight (i.e., homopolymers) of the diisocyanate and up to 99~9 . .
percent by weight of a copolymerizable vinylidene monomer.
DETAILED DESCRIPTION OF THE INVENTIO~
The ethylenically unsaturated blocked aromatic di-isocyanates have the formula R O O
11 11 ' CH2=C-A-OC-N~I-B-NH-C-X . ~: ' wherein R is hydrogen or a methyl or ethyl radical, A is either -a carbonyoxyalkylene radical containing 2 to about 8 carbon atom,s or an aralkylene radical containing 7 to about 12 carbon atoms, ~ -3-,.
. :
B is a bivalent aromatic radical selected from the group consist-ing of arylene, napthalene, and the structure . . .
~~Y~O~
R'n n : ~ , . ., ., ~ . .
:' ' ' ' , . ' .,, '.
" ':
'.'; ~' ' ''' ' ' ~ ' " ~::: .
' :
-3a- .
1C34~
where R is defined as above~ Y is 0, S, or -~-CH2-~-n , n = O
to 3, and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime,benzimi~ole, pyrazole, benzotriazole, caprolactam, thiocaprolactam, or p-nitroaniline. The aromatic rings in A and/or B can be furthersubstituted with 1 to 4 carbon atom alkyl radicals. More preferredly, R is hydrogen or a methyl radical, B is selected from the group consisting of phenylene, tolylene, naphthalene, and the defined structure where Y is ~ CH2-~-n group and n = O to 1.
Examples of the unsaturated blocked aromatic diiso-cyanates are:
When ~rAI~ is a carbonyloxyalkylene radical:
O ' H O O NH-CO-N=C/ 3 ~ t~
CH2-C-CO-(CH2)2-OC-NH ~ CH3 C2H5 .
. CH2=C-CO-(CH2)3-OC-NH ~ NH-cO-N=c~c H
O
CH3 O O NH_co_N=c~ 2 5 CH2=C--CO- (CH2)2-OC-NH~CH3 C6H13 ~ ' , :
H O O O
CH2=C- CO- ( CH2 ) 4-OC-NH~II- C-N~
..~ .
_ 4 _ - . . - . . - . - .
, . . -10~
CH2=C - CO-(CH2)6-OC-NH ~ NH-CO-N-C~ 3 H O O O
CH2=C-CO-(CH2)-0C-NH-C2H4 ~ C2H4-NH-CO-N-C~ 3 ,CH3 ~t ~ <C2H5 CH2=C- CO-(CH2)3-0C-NH ~ . :
NH-C-N ~ ~ ~
' ' ' ' . ' : , , , C,2H5 ,0, ,ol CH3 CH3 ~N ~ CH3 CH2=C- C-(CH2)4-C-NH ~ CH2 ~ H C N ~ : , . :
::, ,.
H O O O . :
~ CH2-C-CO-(CH2)2-0C-NH ~ CH2-NH-C-NH ~ N02 ~ .
.:
O
H O O ~NH-CO-N=C~ 3 -CO-(CH2)4_0C_NH ~ Cl 3 7 ~.
C,H3 ,,~ i ~ 3 ~~ ~
CH2~C - C-(CH2)2-C-NH ~ b H3 < O ~ C2H5 -`.:. :: ' 104i~
O O CH O ~N
, 3 " " ~ 3 CH2=C C0-'CH2'5-OC-NH ~ CH-NH-C-N
O ~
~ ' ,N- N
CH O O NH-C-N~
~ 3 t~ t~
CH2=C CO-(CH2)2-Oc-NH ~ 3 ~ H
CH
H O O ~H-CO-N=C
CH2SC-CO-(CH2)2-OC-NH ~ CH3 2 5 O : ,:
" CH
CH3 O O NH-CO-N=C
CH2=C CO-(CH2)2-OC-NH ~ CH3 C4Hg .
, . ~' CH O O NH-C-N _
3 11 ~ ~
CH?-C - CO-(CH2)2-OC-NH ~ 3 ~ 3 ~.
O
; CH3 ,, tt ~ H-CO-N=C~ 3 CH2=C CO-(CH2)2-OC-NH ~ CH3 '.
.
. .
C,2H5 ,O, o CH3 ' CH2=C _ CO-(CH2)3-OC-~H ~ NH-C-N ~ :
.~
~ ' ' : .:
- .
.:
- : r lQ~O~L
CH O O
, 3 "
CH2=C CO- (CH2)2-OC-NH~CH3,0, ~ ,~, S~ :
t, ~ .
,CH3 i~ ~ H-C-N\
CH2-C CO-CH2CH2-OC- ~ H3 ~ . :
. ~ . . .
' - ...
H O O O
CH2-C-CO-(CH2)4-0-NH ~ CH2 ~ O `~
, CH O O Br ~-CH2=C GO-(CH2)6-OC-NH ~
B NH - C-N-C~ 3 .
C2H5 ., :' " ' CH O O
t 3 CH2=C CO-(CH2)2-0C-NH ~ CH3 ~~ /N CH3 .
NH- C-N
=C-CO-(CH2)4-0C-NH ~ NH C N ~N `
3 ~
~ -. ~
~ . - 7 -.
3 1 ~r ~ ~-- < /=~N
CH2=C--- CO- (CH2)2-0C-NH~cH2~NH-C-N~
~) / <CH3 O / N
H O ~ O j~NH-C~
CH2=C-CO- (CH2)3-0c-NH~ ~ N2 CH3 ;
CH3 0 I N= N
CH2~C - CO-(CH2)2-OC-NH~ NH-C-N~ ¦
<~ ... ~ . ., .
- ,o, ~ . .
CH O O NH-C NH
~ 3 1 r--~
CH2=C CO- ( CH2 ) 2-OC-NH~ 3 [~
NO . .
5 and ~he like.
When l'A" i~ an arylene radical: :
o H O H-CO-N=C~ 3 CH2=c~cH2-oc-NH~cH3 3 ~ .
H ~ 0 ~ It /N1 ~-H2=C~ CH2-OC-NH ~ N~-C-N\=J
.
.
10~0~
CH^ O
CH2=c ~ ~ N -C-N=C~ 3 ; ~
. .
,CH3 ,, .~ = N
CH2=C ~ ~ NH-C-N ~ CH
CH2-OC-NH ~ CH3 ~ 3 ' ,': ~'- ' ' H O CH3~t - -~ ~ CH3 0 ~ .
CH2=C ~ -CH2-OC-NH ~ CH2 ~ NH-C-: 3 '~
-C-~
CH2---O ~ CH2-00-NH ~ H3 (~--H CH2-OC-NH ~ NH-CO-N- C H
CH2-C~ CH3 ' . ~ N2 CH2-oC-NH~CH3 O
.
' ' ~
.: ' - . : .
~ _ g _ '':
1(~4.1l~
CH2=C ~ CH2-OC-NH ~ CH2 ~ NH-C-N
H O ,NH-CO-N-C ~ : .
CH2-C ~ CH2-OC-NH ~ CH3 CH3 C2H5 and the like.
The ethylenically unsaturated blocked aromatic diiso-cyanates are prepared in a two-step process wherein first a hydroxy-containing vinylidene monomer is reacted with an aro-matic diisocyanate, and the product obtained then reacted with a blockIne agent. Reference is made to U.S. Patent 2,958,704, and the process disclosed therein.
The hydroxyl-containing vinylidene monomer has the formula CH2=C-A-OH
where A and R are defined as above. When A is a carbonyloxy-alkylene radical, examples of the monomer include 2-hydroxy-ethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl ethacry-late, 5-hydroxypentyl acrylate~ 5-hydroxy-3-methylpentyl acrylate, 6-hydroxyhexyl acrylate, and the like. When A is an aralkylene or alkyl substituted aralkylene radical, examples include o, m, and p-vinyl benzyl alcohol, o-methyl-p-vinyl benzyl alcohol, and the like, me hydroxyl-containing monomer is reacted with an aromatic diisocyanate using at least a slight molar excess of the diisocyanate. Temperature of reaction is from about 0C. ~ ~ -to 100C. The reaction must be conducted free of water.
~041~
Solvents for the reaction are benzene~ toluene, chlorobenzene, ~-;
chloroform, carbon tetrachloride, trichloroethylene, and the like. The aromatic diisocyanates ha~e the formula OCN-B-NCO
wherein B is defined as above. Examples of these diisocyanates are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphtha-lene-1,4-diisocyanate, diphenyl diisocyanate, diphenylmethane-p,p'-diisocyanate~ dimethylphenylether diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, p-isocyanatobenzyl iso-cyanatel bis(2-isocyanatoethyl)benzene, and the like. Halo-genated diisocyanates such as 1-chloro-2,4-diisocyanatobenzene, tetrachloro-1,3-phenylene diisocyanate, 2,4,6-tribromo-1,3-phenylene diisocyanate, and the like, can be used. ~ ;
The more pre~erred aromatic diisocyanates are those wherein one of the isocyanate groups has a l to 4 carbon atom alkyl group ortho to one of the isocyanate groups. Examples of these are 2,4-toluene diiæocyanate, 2,6-toluene diisocyanate, and ortho-methyl substituents of other aromatic dlisocyanates such as 2-methyl-1,4-naphthalene diisocyanate, 5-methyl-diphenyl diisocyanate, 2,6-dimethyltoluene-1,4-diisocyanate, 3-ethyl-1,4-toluene dlisocyanate, 1,6-dimethyl-2,4-toluene diisocyanate, 3,6-dimethyl-5-ethyl-1,4-naphthalene diisocyanate, and the like.
The ortho-substituted aromatic d~isocy~nates are pre-~erred,as the unhlndered isocyanate group will react first and, pre~erentially, with the hydroxyl group of the monomer. The hindered isocyanate group tends to remain apart from this ~;~ reaction and good yields of the unsaturated aromatic isocyanate are obtained. The product obtained is reacted with a compound havlng a labile hydrogen atom to block the remaining isocyanate group.
30~ The choice of a compound to be used as a blocking age~t is particularly crucial to the successful use of a blocked isocyanate in~nonwoven fiber bonding applications. I~
, ': - 11 ~4~
the blocking agent - isocyanate reaction product is too stable, the agent will not release quickly and/or at moderate tempera- -tures. High temperatures and long heating times can degrade the polymers and the nonwoven fibers. Many tertiary alcohols, phenols, amines, and imines were found to be unsatisfactory for this reason. If the blocking agent - isocyanate reaction product is too labile, the agent will release prematurely and the isocyanate will be free to react. This results in instability of the interpolymer latex or solution and problems in applying snd heat curing. The novel interpolymers of this invention provide an improved balance between polymer stability and quick, moderate temperature cure cycles. This balance is struck and the excellent properties obtained only when a combination of an aromatic diisocyanate and the specified blocking agents are employed.
Blocking agents for the ethylenically unsaturated aromatic diisocyanates are oximes,benzlmidazole, pyrazoles, benzotriazoles, caprolactam, thiocaprolactam, and p-nitro-aniline.
me oximes are aldoximes or ketoximes of the formula H0-N=C
~R"
whereln R' is an alkyl radical containing 1 to about 8 carbon atoms, a cycloalkyl radical containing 4 to 8 carbon atoms, an aryl radical containing 6 to about 12 carbon atoms, or where R' and R", together with the carbon atom, form a carbon ring of 4 to 8 carbon atoms, and R" iæ hydrogen or the same as R'. Examples of the oximes are acetoxime, methylethyl , i ketoxime, methylpropyl ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclohexanone oxime, benzophenone oxime, benzoaldoxime, and the like.
-.:
: .
- 12 - ~
Pyrazole and 1 to 4 carbon atom alkyl substituents thereo~ can be employed. Examples are pyrazole, 3-methyl pyrazole, 3,5-dimethyl pyrazole, and the like.
The benzotriazoles are benzotriazole and 1 to 4 carbon atom alkyl, halogen, and nitro substituents thereof.
Examples of the benzotriazoles are benzotriazole, 5-methyl-benzotriazole, 6-ethylbenzotriazole, 5-chlorobenzotriazole, 5-nitrobenzotriazole, and the like.
The blocking agents are employed on about a 1 to 1 mole basis of isocyanate to agent. The reaction temperature is from about 30C. to about 110C. Reaction time is from about 1 hour to about 15 hours. Suitable solvents for the reaction are aromatic hydrocarbon solvents such as benzene and toluene.
The ethylenically unsaturated blocked aromatic diisocyanates can be polymerized using emulsion (latex), suspension, solution~ and bulk techniques known to those skilled in the art. The polymerization can be performed as a batch reaction~ or one or more ingredients can be propor-tioned during the run. Temperature of polymerization ranges from about -lO~C. to about 100C., whereas a more preferred range is from about 5C. to about 80C.
The polymerization is initiated by free-radical generating agents. Examples o~ such agents are organic peroxides and hydroperoxides such as benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, paramethane hydroperoxide, and the like, used alone or with redox systems; dlazo compounds such as azobisisobutyronitrile, and the like; persulfate salts such as sodium, potassium, and ammonium persulfate, used alone ~ .
1~4i~0~
or with redox systems, and the use of ultraviolet light with photo-sensitive agents such as benzophenone, triphenylphosphine, organic diazos, and the like.
Typical emulsion polymerization ingredients would include a persulfate salt or organic peroxide and uqually a redox system, water adjusted to a desired pH with acids or bases and usually buffered with inorganic salts and either anionic, cationic, or nonionic surface active agents well known to the art. -The polymerization normally is continued until about 90% or more conversion of monomers is obtained. The resulting latex can be coagulated to isolate the polymer. Typical coagulation procedures are salt/acid coagulations, use of polyvalent metal salts such as MgS04, use of alcohols such as methanol and isopropyl alcohol, and freeze agglomeration techniques. The polymer is then usually washed wlth water and dried. -The polymers are comprised of~rom 0.1 percent to 100 percent by weight (i.e., homopolymers) of an ethylenically unsaturated blocked aromatlc diisocyanate(s), as defined, and up to 99.9 percent by weight, and more preferably up to about 70 percent by wei~ht, o~ a copolymerizable vinylidene monomer.
Thls monomer is a vinyl monomer having a terminal vinylidene ;
(CH2=C-) group. Examples o~ these monomers are acrylates and methacrylates such as ethyl acrylate, n-butyl acrylate, octyl acrylate, dodecyl acrylate, methyl methacrylate, phenyl acrylate, cyclohexyl acrylate, and the like; vinyl and allyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, and the like; vinyl ketones such as methyl vinyl ..
ketone? propyl vinyl ketone, and the like; vinyl and allyl ethers such as vinyl methylether, vinyl ethylether, vinyl . . .
isobutylether, allyl methylether, and the like; vinyl aromatics .
1(~41~Ql ;
such as styrene, ~-methylstyrene, p-chlorostyrene, vin~l toluene, vinylnaphthalene, and the likej vinyl nitriles such as acrylonitrile, methacrylonitrile, ~-chloroacrylonitrile, and the like; dienes such as butadiene, isoprene, chloroprene, 2-isopropyl-1,3-butadiene, and the like, ~-monoolefins such as ethylene, propylene, l-butene, l-hexene, and the like;
vinyl halides such as vinyl chloride, vinyl fluoride, vinyl-idene chloride, and the like; and divinyls such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, and the like. In addition, because the isocyanate is blocked, so-called reactive monomers can be copolymerized with the acrylates and unsaturated lsocyanate. Examples of these monomers are vinyl carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, 2-hexanoic acid, and the like, vin~l amides such as acrylamide, methacrylamide, N-methyl methacrylamide, dlacetone acrylamide, and the like; hydroxyl-containing vinyl monomers such as allyl alcohol, vinyl benzyl alcohol, ~- ;
hydroxyethyl acrylate, ~-hydroxypropyl acrylate, 4-hydroxy-butyl acrylate, ~-hydroxyethyl methacrylate, N-methylol acrylamide, and the like.
The polymers are high molecular welght solids having dllute solution viscosities (DSV) of over 0.5 measured on a 0.2 gram sample of the polymer in 100 milliliters of solvent at 25C. The polymers are cured at temperatures as low as 80C. and can be cured under acidic, neutral, or basic pH
conditions.
, . .
The polymers can be admixed with cure ingredients and compounding ingredients using two-roll mills, internal mixers ; such as Banburys and extruders, and like equipment.
~ The polymers, as isolated solid rubbers, can be - cured to prepare useful vulcanizates. Compounding ingredients well known to the art can be used, such as fillers, oils and ~ 15 -.,.: . . - - ~
~ 041~0iL
plasticizers, antioxidants, and the like. Standard mixing and cure techniques are employed. Upon heating the polymer, the blocking agent is released. Hydroxyl, carboxyl, and amine containing materials are used as curing agents. For example, glycols, polyols, polyalkylene amines, hydroxyl and carboxyl containing polyesters and polyethers, hydroxyl, carboxyl, and amine terminated vinylidene polymers, etc., and water itself, are all known and suggested reactants for iso-cyanate-containing materials. If the interpolymer itself contains hydroxyl, carboxyl, or amine groups, the polymer can be considered self-curing. Upon heating, the isocyanate is released and the polymer can undergo intra- and inter-molecular crosslinking.
The polymers do not have to be isolated, but can be readily stored in latex or solution form. The novel polymers have excellent stability in latex form. In non-woven binder applications, the polymers are conveniently used as latexes or solutions to coat or impregnate the fibers. Fillers, extenders, and other ingredients such as stabilizing agents, thickeners, antioxidants, and the like, are readily admixed with the latexes or solutions prior to u~e.
In non-woven flber binder applications, the ethylen-ically unsaturated bl~ked aromatic diisocyanates are preferably copolymerlzed with an acryiate monomer. The interpolymer com-prises from about 0.5 percent to about 50 percent by weightof the diisocyanate(s) as defined, and from about 50 percent to about 99.5 percent by weight o~ an acrylate monomer(s).
More preferably, the interpolymer contains from about 1 percent to about 30 percent by weight of the diisocyanate, from about 70 percent to about 99 percent by weight of an acrylate monomer, and up to 20 percent by weight of another copol~merizable .. .: .. ..
vinylidene monomer, all present as interpolymerized units.
.
~U4~
The acrylate monomer has the formula CH2=C- C~Ra wherein R is H, -CH3 or -C2H5~ and Ra is an alkyl radical containing 1 to about 24 carbon atoms, an alkoxyalkyl or alkylthioalkyl radical containing a total of 2 to about 12 carbon atoms, or a cyanoalkyl radical containing 2 to about 12 carbon atoms total. The alkyl structure can be linear or branched Examples of the acrylates are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl ~
acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, ~ -2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-tetradecyl acrylate, n-octadecyl acrylate, n-eicosyl acrylate, and the like, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, n-octadecyl meth-acrylate, ethyl ethacrylate, n-butyl ethacrylate, and the like, methoxymethyl acrylate, methyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl .
acrylate, methoxyethyl methacrylate, methylthioethylacrylate~
hexylthioethyl acrylate, and the like; and a and ~-cyanoethyl acrylate, a, ~, and ~-cyanopropyl acrylate, cyanobutyl acrylate, cyanohexyl acrylate, cyanooctyl acrylate, cyanoethyl meth-; acrylate, and the like. O~ten mixtures of two or more monomers ~ and/or types o~ acrylate monomers are employed.
-~ 25 More preferably, the interpolymer contains from 70 percent to about 99 percent by weight o~ an acrylate monomer(s) whereln Ra is an alkyl radical containing 1 to about 18 carbon atoms or an alkoxyal~yl radical containing 2 to about 8 carbon atoms. Examples of the more preferred monomers are methyl acrylate, ethyl Icrylate, n-propyl acrylate, isopropyl acrylate, ~ n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl ;~ _ 17 acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, methoxyethyl acrylate, ethoxy-ethyl acrylate, methoxypropyl acrylate, ethoxypropyl acrylate, and the like. Both an alkyl acrylate and an alkoxyalkyl acrylate can be used. Especially good results are obtained when employing ethyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and/or methoxyethyl acrylate.
The interpolymers are applied to the non-woven fibers using dip coating, knife edge coating, roller coating, soaking, spray coating, and like known techniques. Cure conditions depend in part upon the specific blocking agent and aromatic diisocyanate used to prepare the monomer. However, temperatures from about 80C. to about 150C. and more preferably from about 100C. to about 125DC. are usually employed. Cure times range from about 3 minutes to about 30 minutes. An excellent cure is readily obtained at 100C. in about 3 minutes at an acidic, neutral or basic pH.
Examples o~ non-woven fibers are papers such as Kraft paper, crepe paper, and the like, rag fibers, cotton, wool, regenerated cellulose, glass fiber, asbestos, and synthetic fibers such as polyesters~ and the like. In addition to binding fibers to impart tensile strength, edge tear strength, and the like, the lnterpolymers are also use~ul as pigment and filler binders and as fabric adhesives.
The polymers can be copolymers of the essential blocked diisocyanate with acrylate monomers and from about ~ .....
0.5 percent to about 10 percent by weight of a hydroxyl, carboxyl, amlne or amide containing monomer. ~fter applying such an interpolymer to a non-woven substrate and heating it~
the blockingagent is released and the free isocyanate cross-links through these reactive groups to cure the polymer. -However, if the polymer does not have these groups present thereon, compounds containing the groups can be readily added to the latex or solution prior to use. These compounds are crosslinking agents, and include aliphatic and phenolic diols and polyols, diamines and polyamines~ di- and polymercaptans, di- and polycarboxylic acids, and polymeric materials such as polyether polyols, polyester polyols, polyester amides, poly-ether amides~ and the like. Examples o~ crosslinking agents are alkylenediols such as 1,4-butanediol, 1,6-hexanediol, 4-methyl-1,4-pentanediol, l,10-decanediol, and the like; ali-cyclic diols such as 1,4-cyclohexanediol, 2-hydroxymethyl-cyclohexanol, and the like; phenolic diols such as p hydroxy-benzyl alcohol, hydroquinone, 2,2'-dihydroxydiphenyl, methylene-bisphenol, p,p'-isopropylidene bisphenol, and the like; polyols such as 1,3,5-pentanetriol, 1,3,5-trishydroxybenzene, glycerol, sorbital, and the like; alkylenediamines such as ethylene-diamine, 1,2-butylenediamine, 2-methyl-1,4-diaminobutane, hexamethylenediamine, decamethylenediamine, dodecamethylene-diamine, and the like; alicyclic diamines such as 1,4-diamino-cyclohexane, 1,4-diaminoethylcyclohexane, and the like; aro-matic diamines such as m-phenylenediamine, m-xylylenediamine, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, p,p'-bis-aminomethyl diphenylmethane, and the like, heterocyclic dl-amines such as piperazine, aminoethylpiperazineg and the like;
polyamines such as diethylenetriamine, triethylenetetraamine, and the like; and alkanolamines such as tris(hydroxyethyl) amine, bisthydroxyethyl)methylamine, tris(hydroxypropyl)amlne, l-amino-2-hydroxypropane, l-aminomethylcyclohexanol, m-amino-phenol, 2-amino-6-hydroxypyridine, and the like. The more pre~erred crosslinking agents are the alkylenediols, the alk~lenediamines, and the alkanolamines.
The crosslinking agent can be added directly to the latex (or solutionj. It can be dissolved in a solvent such ~(~4~L~Q~
as chloroform or trichloroethylene, or suspended in water using an emulsifying agent, and then added to the latex or solution. No reaction takes place until the blocking agent is released in the cure process. The crosslinking agents are used on about a mole to mole basis of isocyanate to hydroxy, amino, etc., group. Higher levels may be used, but it is not necessary for obtaining fast strong cures.
Of course, water alone can act as a crosslinking agent for the polymers. In the presence of water, the blocked diisocyanate can react to form an amine structure which can then further react with another blocked diisocyanate group to crosslink the polymer. The water can be added to the polymer, or it can be present as residual water in the polymer or saturated non-woven. Atmospheric moisture can also act to ; -crosslink the polymers.
As the novel interpolymers have particular utility as binders for nonwoven fibers, testing was directed to evaluation of the interpolymers in latex form as paper saturants. Actual testing included original and wet tensile strength, using an Instron tensile tester at a pull rate of 12 inches per minute. Wet tensile followed TAPPI procedure T465-m44 (specimens soaked in water for 16 hours before teGting).
The following examples serve to more fully illustrate the invention. .
EXAMPLE I
A series o~ ethylenically unsaturated blocked aro-matic diisocyanates was prepared. The general reaction scheme is to first react a mole of a hydroxyl-containing vinylidene monomer with about two moles of an aromatic diisocyanate, and secondly, react the intermediate product with about 1.1 mole of a defined blocking agent per mole of the intermediate.
. Preparation of 4-(0-methacryloyloxyethyl)-.
1~4~
urethanotolyl(2-carbamoyl)-1-tolyltriazole. The synthesis consists o~ a two-step reaction. Toluene, 1080 grams and 2,4- -toluene diisocyanate~ 1160 grams (6.66 moles), were put into a reactor vessel equipped for stirring and temperature control.
The vessel was then flushed with nitrogen ~as and the inter-mediate product reaction conducted under nitrogen gas. The mix was heated to 60C. while stirring, and 433 grams (3.33 moles) of ~-hydroxyethylmethacrylate slowly added over 5.5 hours. Temperature o~ the mixture rose to 65~C. and was con-trolled there throughout the addition. The mixture was thenstirred for one hour. Total reaction time was about 7 hours.
The reactor mixture (a solution)was cooled to 5C.
and allowed to stand ~or about 16 hours. White crystals formed in the solution. me mixture was then cooled to -30C. and the crystals filtered out and washed with hexane. The inter-mediate product was dried to yield 754 grams o~ a white crystalline solld having a melting point of 71-72C. Analyzed ~or isocyanate content and for unsaturation, the intermediate product proved to be about 99% pure. The yield was 74~ by 20 ~ ~ weight based on the theoretical weight as measured on the hydroxy compound.
The intermediate product (i.e., the ~-hydroxyethyl-methacrylate/2,4-toluenediisocyanate reaction product), 22.3 .
grams (0.0735 mole) was dissolved in 350 milliliters o~
toluene at about 30C. and the solution placed into a reactor vessel., Tolyltriazole, 10.75 grams (o.o808 mole) was dissolved in 50 milliliters of toluene at about 30C. and the solution then~added to the reactor vessel. The mixture was stirred for 3~hours at 30~C. and then at 50C. for 0.5 hour. A white 3~ precipltate forms during the stirring time. Total reaction time is about 4 hours. -- The reaction mixture was cooled to 0C. and the white ~ ~ .
.
~ ~ .
~(~4~
precipitate isolated by filtration. The product was washed with acetonitrile and dried at 25C. under a vacuum to yield 25.6 grams of a crystalline solid having a melting point of 132-133.5C. The yield was 80~ based on the amount of inter-mediate product used. Analysis by unsaturation showed theproduct to be about 99% pure. The product has the structure O N=N~
CH3 O O NH-C-N~
CH2=C - COCH2CH2-OC-NH ~ CH3 ~
B. Preparation of 4-(0-mPthacryloyloxyethyl)ure-thanotolyl(2-carbamoyl)-2-butanone oxime. The intermediate -product prepared above was employed.
Toluene, 2686 milllliters, and 517 grams (1.7 moles) of the intermediate product were placed in a reactor vessel and stirred. Methylethyl ketoxime, 152 grams (1.74 moles) was dissolved in 260 milliliters of toluene and the solution ~ `
added to the reactor vessel slowly over a 1.5 hour period.
Temperature of the reaction was kept at 28-290C. The mixture was then stirred for 16 hours at about 25C., followed by cooling to -30C. A white preclpltate formed whlch was flltered out and dried to yleld 494 grams of product (a 74%
yield). The crystalline product has a melting point of 80.50-820C., and analyzed by unsaturation to be about 98% pure.
The theoretlcal nltrogen content of the product is 10.7~ by weight and the analyzed nitrogen content was measured to be 10.6~ by weight. The product has the structure .
,~ C2H5 ~ ,CH3 1t ~ NH-CON=C
CH2-C - COCH2CH2-OC-NH ~ CH3 CH3 :
Ql C. Following the procedure given in B above, the ~ollowing compound was prepared by reacting the intermediate product with acetoxime:
" ,CH3 CH O O NH-CON=C
~ 3 ~ r--<
CH2~C - COCH2CH2-OC-NH ~ 3 H3 D to E. Following the procedure given in B, the inter-mediate product was reacted with meth~lisobutyloxime and di-methylpyrazole, respectively, to yield:
,0, Cl H2 . .:
t~ It CH2=C COCH2CH2-OC-NH ~ CH3 CH3 melting point o~ 75-79.5C., and O / ~ H3 CH3 ,0, ,, ~ NH-C-N
CH2-C COCH2CH2-OC-NH ~ CH3 CH3 melting point of 109-110.5C.
F. Followlng the procedure glven in A above~ ~-hydroxyethyl acrylate and 2,4-toluene dlisocyanate were reacted together to form an intermedlate product which was then reacted with methylethyl ketoxime. The product is ~; O ,C2H5 ', '.
H O O~ ~ H-CON=C
CH2-C-COCH2CH2-OC-NH ~ CH3 CH3 melting point of 1~08-113C. The compound was tested to be 95% pure using a standard isocyanate analysis test.
G. Following the procedure given in A æbove, ~
. ' ' "
- 23 - ~
Q~
p-vinylbenzyl alcohol was reacted with 2,4-toluene diisocyanate, followed by reaction with methylethyl ketoxime. The product is . ~ .
o C2H5 H O NE-CON=C
CH2 C ~ CH2-OC-NE ~ CH3 CH3 melting point of 79.5~-83C.
FXAMYLE II
The ethylenically unsaturated blocked aromatic di-isocyanate prepared ln Example I in procedure B was inter- ~ - :
polymerized with a vinylidene terminated monomer, using an emulsion polymerization system. The recipe is as follows: - i Ethyl acrylate grams 94.1 `
Diisocyanate B~ grams 5.9 Water, milliliters 175 Sodium lauryl sulfonate 30 millilitersb N~halene sbulfonate, 9 milliliters Sodium hydrosulfite, 8.3 , millilitersC, Sodium formaldehyde sulfoxalate, 10 millilitersd Sodium salt of ethylene diamine 8.3 tetraacetic acid and sodium gluconate, milliliterse p-methane hy~roperoxide, 0.2 millilitersl O
CH3 O O H-coN=c~ 2E5 a CH2=C - COCH2CH2-OC-NE ~ CH3 CH3 b 10% by weight in water ;
c o,5% by weight in water d 1.0% by weight in water .
e 0.24 and 0.13 grams in 100 milliliters of water f 50~ by weight The dlisocyanate was dissolved in the ethyl acrylate, and the solution admixed with the water, sodium lauryl sulfonate, ".. '.
- ' ~:, - .
.. . ... .. . ~ . ~ , ~,. ., , , .. - .
sodium hydrosulfite, and naphthalene sulfonate. 17 milliliters of the mixture was placed in a reactor vessel followed by the sodium formaldehyde sulfoxalate, sodium salt of ethylene diamine tetraacetic acid and sodium glyconate, and p-menthane hydroperoxide~ An immediate exotherm occurred and temperature of the reaction was controlled at 27~3C. Using a stirred dropping funnel, the remaining mixture was slowly added to the reactor vessel over a 1 hour period. After the addition was complete, the reactor mix stood for 16 hours. Total conversion of monomers to polymer was 96%, based on the total solids of the mix.
EXAMPLE III
Interpolymers of ethylenically unsaturated blocked aromatic diisocyanates (as prepared in Example I) and ethyl acrylate, were prepared following the procedure of Example II.
The ~ollowing polymeric samples were prepared and evaluated in thelr latex form.
.
' :
N 1~ C ~ m ~i~ V- ~- V U- ~- U V--V--V--V
o= V ~ o- V ,~ O- V ~ U o ~I z Oo _ V o _ V o = V o- o , ~ , rlU V V V ' ' ~v~ ~ ~ . u o- VO Ot V o C~ O- U . .
N ~ P l : :~` .3 ,,~
. ~ .~ ` ` .
.. . ~ . .
I ~ 11 14~
æ ~N ~ N
o~ o ~d 5~ ~ O O = C~
a) ~; 1o = ~ ~ , ~ ~ -I P~ ~ V a) ~PJ~ . ~
o ~
o æ
p~ o= O ~ o ~ .
P~
~ ~ 1 o Or ~
, ~ , , o . .:
: ' -o ", . ~ ,..
C) C) . ~, . . .
o~
:
-- h C) ~ ' '., .
~ ' ,, .
' ' ' ' '- ' ~, ' ' .
' ' .
~ . , .. .
The latex samples were used at a total solids content ...... .. .
of about 20% by weight. The non-woven ~iber employed was saturatlon grade, bleached Kraft paper of 11 mils thickness.
8 inch by 1 inch strips of the paper were soaked in each sample latex. Solids pickup was about 50~ by weight for each test strip. The strips were then dried at room temperature followed by curing at selected temperatures and times. When an added crosslinker was employed, it was dissolved in or added to the latex as a solution or suspension prior to soaking I0 the paper strips.
Evaluation consisted of wet tensile strength testing following Tappi procedure T465-m 44. The impregnated paper strips were soaked overnight in water and then pulled on an . . , :, .
Instron tensile tester at a ~aw speed of 12 inches per minute.
Test strip samples were run in triplicate and the arithmetric average reported.
The crosslinker employed in this series o~ experi-ments i8 either residual water (i.e., no crosslinking agent was added~ or triethanol amine. When triethanol amine was used, it was simply dissolved in the latex, prior to soaking the samples? at none, one, or two mole equivalent~ of cross-linker per mole equivalent o~ isocyanate group on the polymer.
The data obtained is listed in the ~ollowing table.
Wet Tensile Strength Latex Part~ by Wt. of 3 Mlnute Cure At Sample Triethanol aminea 100C. 125C. 150C.
none 18 20 20 0.75 21 20 21 1.50 22 20 22 3 B none 20 22 23 1.~0 22 24 25 C none 15 21 27 0.?5 18 23 29 , . .
D none 20 22 21 3~ - 0.75 20 21 21 , f l~ L101 Wet Tensile Strength Latex Parts by Wt. of 3 Minute Cure At Sample Triethanol Aminea 100C. 125C. 150C.
E none 22 23 24 1.50 20 23 22 F none 21 22 23 0.75 21 24 24 G none 19 23 22 0.75 20 23 24 aParts by weight per 100 parts by weight of polymer in the latex The data shows that excellent wet tensile strength is exhibited by all of the æamples. The paper strip, without -. .
being impregnated by the novel polymers, has a wet tensile ~-strength of about 0.5 psi. The Example shows the excellent -results obtained using the novel polymers in latex form as non-woven fiber binders. me strength obtained is as good as or better than results obtained using commercial latexes, especially at low cure temperatures. For comparison, a commercial acrylic latex would exhibit, cured at lOO~C. using no crosslinker, a wet tensile strength of about 4 psi at a basic pH to a high of about 16 psi at an acid pH.
EXAMPLE IV
Following up Example III in more detail, sample latex A was used to prepare wet tensile ~amples at various pH's of the latex. Using 0.90 parts by weight of 1,6-hexane-dlol as a crosslinker, after cure at 100C. for 3 minutes, the wet tensile strength values were: pH of 5, 20 p8i, pH of 7, 20 psi, and pH of 9, 19 psl. Repeating the test using 0.75 ~ parts by weight of triethanol amine as the crosslinker, the values were: pH of 5, 21 psi; pH of 7, 21 psi; and pH of 9, 21 psi. In contrast, two commercial acrylic latexes were also evaluated as to their ability to impart wet tensile strength over a range of pH values with the following results: p~I of 5, .
, , ., - - . :
- 29 ~
~.L~Ql 11 psi and 6 psi, respectively; pH of 7, 8 psi and 6 psi~
respectively; and pH of 9, 4 psi and 4 psi, respectively.
The exam~le shows that not only do the polymers of the invention impart greater wet tensile strength to non-wovens than known commercial latexes, compared at a 100C. cure temperature, but the novel polymers are also not sensitive to pH as the commercial acrylic latexes are. At a cure temperature :
of 80C., a test sample using the novel polymer prepared as sample B had a wet tensile strength of 14 psi (cured 3 minutes). ~
The difference between the novel polymers of the invention - ~, and the commercial latexes diminishes as the temperature of cure increases and the pH of cure decreases. However, fast :
cures at low temperatures over a range of pH conditions is highly desirable.
. . .
EXAMP~E V
The ultimate tensile strength and wet tensile strength of a bound non-woven fiber is a function of both the polymeric binder and the crosslinking agent employed. Of the known crosslinking agents, the use of alcoholic amines is preferred with the novel polymers of this invention. Using the polymer latex prepared as sample A in Example III, and following the procedure given in Example III, various cross-linking agents were evaluated at one equivalent weight as to their abillty to develop rapid and high strength cures.
. .
Ql ~ ~
.: - . . .
~, o ~C--O ~ ~-.l C~J N N cu c~l ~ ~1 ":':
o u~ C~ N C~ N N ~1 ~1 rl . .. :
~ O ~ ~ ~ ~1 ~1 ~ CU ~ "
O ~1 ~I N ~ C~J C~ ~I h ;-a~ ~1 . ~ .. .
E~ h ol ~0 o ,I N o ~3: X) l ~1 ~1 ~ ~I N c~
o : :
~ ~ o bD "' ~`"''' . .
. . o 0~ 1~ 0 00 0 ~ rl h . .... , . ~q o ~R O ~ O O O
a~ . ~
P~ ~ o : . ., o O ~ h . ~ ~ ~ ~r O O r~
~: ~E c h r~ O ~r ~:! r ~ a) ~q .
O ~rl ~ ~ Ci ~r~ ~C
O ~ r ~ ~3 a ~ ~:! O r~ a) r~ cq h,r-l - ~d c~ ~ O ~1~ n~ ~ a 5 . a) ~ c~ o o rl ~ 5'~ ~ ~ ~ O ~ ~q 5'~ ::
~0 O . I O (1~ ~ 5 N ~Q Ul t~ h - O 5~0 r1~ ~ r~ rl h O ~ ~ h ~rl C) ~ r~
C,) ~z; r-l r~ ) r~ cB ~ C) .~ ~ - : '' - " ' ' r~
r~ 0 ~ ,..... ..
:. , ; . .:
:: :
` ~: . ~: :
::
EXAMPLE VI
The polymers of the present invention present a unique balance between rapid cure at low temperatures (evidencing quick, efficient release of the blocking agent) and stability, especially to hydrolysis in the presence of water. This unique balance is struck by the use of both the aromatic dilsocyanate and the specified blocking agents in the preparation of the novel ethylenically unsaturated blocked aromatic isocyanates. The following data shows that the polymers of the invention have good stability to hydrolysis.
Polymer latex sample B prepared in Example III is employed. ~
Testing consisted of wet tensile strength before and after ;
aging at room temperature.
Wet Tensile Sample B Strength, psi Time Aged Test Strip Cl~rginal Aged (days) ~;
.:
Cured ~i 3' at 100C. 20 14 50 -;
3' at 125C. 22 19 50 3' at 150C. 23 19 50 Aged in presence 0~ 0.75 parts by wt. of triethanol amine Cured 3' at 22 19 50 100C. 22 17 100 3o EXAMPLE VII
Expanding on Example VI, other polymers o~ this invention were prepared following the procedures given in Examples I and II, and evaluàted as to their stability to hydrolysis and their ability to impart wet tensile strength to non-woven flbers. Original and aged wet tensile strength ~ . - .
of impregnated non-woven paper was determined following the ~ - 32 -1~4~ Q~ :
procedure in Example III. Results are reported in the following tables.
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V V V V V V V ~ ~
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. o o o o vl ~ ~
C~- V , V- V
V- V ..
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~ .o~ ~o h 00 ~ :
a~
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P:~ H ~
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~ v- v v- v- v o o-v ~
l ~ o ~ ~ o q o = ~ ~ :
~d~ ~
~ o- v l l ~ :
c) o o- v o- v o l o o ~
V ~ ~ ~:
~ p:~ P:~
o v v o- v o o ~
I o I o p~
v v o ~ :
~ ~ .. .
: ~ . ll :~ ~ ~
~ o ~ :
~ . tq ~ : p~
~O O o o F~ h ~, h P~
~ bD ~
O ~ 1~1 ¢
~ ;~
~ .
O : .: ' ' P~ . . ~
. ' :: , .~ .
:.
' ~
- 35 ~
- ; , .. . . ~ ~ . , ...... .: ~ . . , . ~ .. . . . .. . . . .. . . .
The polymers above, in latex form, were used to impregnate saturation grade, bleached Kraft paper (11 mils thick) ~ollowing the procedure in Example III. The test sample strips were then evaluated for their original wet tensile strength. Following Example VI, after allowing the polymer latex samples to age, test sample strips were again prepared and the wet tensile strength measured. Results are reported below.
Wet Tens~le Average Latex Stren~th , psi % Decrease -Sample Original Aged ays Per Day B 20 12 100 0.40 H 20 17 45 0.33 14 100 0.30 J 20 17 30 0.50 0.42 K 162 11 34 0.92 6~ 0.45 M 223 15 5 o.64 ' 1 Cured 3 minutes at 100C., no crosslinker added 2 At 15th day 3 At 70th day The data shows that the polymers of the present invention, samples B and H to M, prepared using the novel ethylenlcally unsaturated blocked aromatic diisocyanates, im~art good wet tensile strength to non-woven flbers, and have unexpectedly good stability to hydrolysis when stored as a latex. If a crosslinker and/or higher cure temperatures are employed with the novel polymers, higher original and aged wet tensile strengths are obtained. For example, sample I, which showed the least stability, can be cured at 150C. using 0.75 parts o~ triethanolamine (after 47 days of aglng) to yield , - ~
~ - 36 -.~, ' :. ..
a wet tensile strength of 19 psi.
EXAMPLE VIII
If, instead of reacting the hydroxyl-containing monomer with the aromatic diisocyanate, the blocking agent is first reacted with the aromatic diisocyanate, different variations in the structure of the ethylenically unsaturated blocked aromatic diisocyanate can be prepared. For example, in Example I, procedure A, the following diisocyanate was prepared:
.. N--N
CH3 0 0 ~ H-C-~
CH2=C - COCH2CH2-OC-NH ~ 3 ~
When the methylbenzotriazole was first reacted with the 2,4-toluene diisocyanate, followed by reaction with the ~-hydroxy-ethyl acrylate, the structure is:
CH3 0 o " "
CH2~C - COCH~CH2-OC-N ~ " /N= N
CH3 ~ NH-C-N
~ CH3 me diisocyanate prepared by the reverse addition ;l ;
o~ materials can be easily polymerized with vinylidene-termin-ated monomers via emulsion techniques, and is useful in latex iorm as a binder ~or non-woven ~ibers. The following data shows this fact.
Latex Wet Tensile Strength~ psib ::
pa 15 16 19 22 :' .
a 96% by weight ethyl acrylate,
CH?-C - CO-(CH2)2-OC-NH ~ 3 ~ 3 ~.
O
; CH3 ,, tt ~ H-CO-N=C~ 3 CH2=C CO-(CH2)2-OC-NH ~ CH3 '.
.
. .
C,2H5 ,O, o CH3 ' CH2=C _ CO-(CH2)3-OC-~H ~ NH-C-N ~ :
.~
~ ' ' : .:
- .
.:
- : r lQ~O~L
CH O O
, 3 "
CH2=C CO- (CH2)2-OC-NH~CH3,0, ~ ,~, S~ :
t, ~ .
,CH3 i~ ~ H-C-N\
CH2-C CO-CH2CH2-OC- ~ H3 ~ . :
. ~ . . .
' - ...
H O O O
CH2-C-CO-(CH2)4-0-NH ~ CH2 ~ O `~
, CH O O Br ~-CH2=C GO-(CH2)6-OC-NH ~
B NH - C-N-C~ 3 .
C2H5 ., :' " ' CH O O
t 3 CH2=C CO-(CH2)2-0C-NH ~ CH3 ~~ /N CH3 .
NH- C-N
=C-CO-(CH2)4-0C-NH ~ NH C N ~N `
3 ~
~ -. ~
~ . - 7 -.
3 1 ~r ~ ~-- < /=~N
CH2=C--- CO- (CH2)2-0C-NH~cH2~NH-C-N~
~) / <CH3 O / N
H O ~ O j~NH-C~
CH2=C-CO- (CH2)3-0c-NH~ ~ N2 CH3 ;
CH3 0 I N= N
CH2~C - CO-(CH2)2-OC-NH~ NH-C-N~ ¦
<~ ... ~ . ., .
- ,o, ~ . .
CH O O NH-C NH
~ 3 1 r--~
CH2=C CO- ( CH2 ) 2-OC-NH~ 3 [~
NO . .
5 and ~he like.
When l'A" i~ an arylene radical: :
o H O H-CO-N=C~ 3 CH2=c~cH2-oc-NH~cH3 3 ~ .
H ~ 0 ~ It /N1 ~-H2=C~ CH2-OC-NH ~ N~-C-N\=J
.
.
10~0~
CH^ O
CH2=c ~ ~ N -C-N=C~ 3 ; ~
. .
,CH3 ,, .~ = N
CH2=C ~ ~ NH-C-N ~ CH
CH2-OC-NH ~ CH3 ~ 3 ' ,': ~'- ' ' H O CH3~t - -~ ~ CH3 0 ~ .
CH2=C ~ -CH2-OC-NH ~ CH2 ~ NH-C-: 3 '~
-C-~
CH2---O ~ CH2-00-NH ~ H3 (~--H CH2-OC-NH ~ NH-CO-N- C H
CH2-C~ CH3 ' . ~ N2 CH2-oC-NH~CH3 O
.
' ' ~
.: ' - . : .
~ _ g _ '':
1(~4.1l~
CH2=C ~ CH2-OC-NH ~ CH2 ~ NH-C-N
H O ,NH-CO-N-C ~ : .
CH2-C ~ CH2-OC-NH ~ CH3 CH3 C2H5 and the like.
The ethylenically unsaturated blocked aromatic diiso-cyanates are prepared in a two-step process wherein first a hydroxy-containing vinylidene monomer is reacted with an aro-matic diisocyanate, and the product obtained then reacted with a blockIne agent. Reference is made to U.S. Patent 2,958,704, and the process disclosed therein.
The hydroxyl-containing vinylidene monomer has the formula CH2=C-A-OH
where A and R are defined as above. When A is a carbonyloxy-alkylene radical, examples of the monomer include 2-hydroxy-ethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl ethacry-late, 5-hydroxypentyl acrylate~ 5-hydroxy-3-methylpentyl acrylate, 6-hydroxyhexyl acrylate, and the like. When A is an aralkylene or alkyl substituted aralkylene radical, examples include o, m, and p-vinyl benzyl alcohol, o-methyl-p-vinyl benzyl alcohol, and the like, me hydroxyl-containing monomer is reacted with an aromatic diisocyanate using at least a slight molar excess of the diisocyanate. Temperature of reaction is from about 0C. ~ ~ -to 100C. The reaction must be conducted free of water.
~041~
Solvents for the reaction are benzene~ toluene, chlorobenzene, ~-;
chloroform, carbon tetrachloride, trichloroethylene, and the like. The aromatic diisocyanates ha~e the formula OCN-B-NCO
wherein B is defined as above. Examples of these diisocyanates are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphtha-lene-1,4-diisocyanate, diphenyl diisocyanate, diphenylmethane-p,p'-diisocyanate~ dimethylphenylether diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, p-isocyanatobenzyl iso-cyanatel bis(2-isocyanatoethyl)benzene, and the like. Halo-genated diisocyanates such as 1-chloro-2,4-diisocyanatobenzene, tetrachloro-1,3-phenylene diisocyanate, 2,4,6-tribromo-1,3-phenylene diisocyanate, and the like, can be used. ~ ;
The more pre~erred aromatic diisocyanates are those wherein one of the isocyanate groups has a l to 4 carbon atom alkyl group ortho to one of the isocyanate groups. Examples of these are 2,4-toluene diiæocyanate, 2,6-toluene diisocyanate, and ortho-methyl substituents of other aromatic dlisocyanates such as 2-methyl-1,4-naphthalene diisocyanate, 5-methyl-diphenyl diisocyanate, 2,6-dimethyltoluene-1,4-diisocyanate, 3-ethyl-1,4-toluene dlisocyanate, 1,6-dimethyl-2,4-toluene diisocyanate, 3,6-dimethyl-5-ethyl-1,4-naphthalene diisocyanate, and the like.
The ortho-substituted aromatic d~isocy~nates are pre-~erred,as the unhlndered isocyanate group will react first and, pre~erentially, with the hydroxyl group of the monomer. The hindered isocyanate group tends to remain apart from this ~;~ reaction and good yields of the unsaturated aromatic isocyanate are obtained. The product obtained is reacted with a compound havlng a labile hydrogen atom to block the remaining isocyanate group.
30~ The choice of a compound to be used as a blocking age~t is particularly crucial to the successful use of a blocked isocyanate in~nonwoven fiber bonding applications. I~
, ': - 11 ~4~
the blocking agent - isocyanate reaction product is too stable, the agent will not release quickly and/or at moderate tempera- -tures. High temperatures and long heating times can degrade the polymers and the nonwoven fibers. Many tertiary alcohols, phenols, amines, and imines were found to be unsatisfactory for this reason. If the blocking agent - isocyanate reaction product is too labile, the agent will release prematurely and the isocyanate will be free to react. This results in instability of the interpolymer latex or solution and problems in applying snd heat curing. The novel interpolymers of this invention provide an improved balance between polymer stability and quick, moderate temperature cure cycles. This balance is struck and the excellent properties obtained only when a combination of an aromatic diisocyanate and the specified blocking agents are employed.
Blocking agents for the ethylenically unsaturated aromatic diisocyanates are oximes,benzlmidazole, pyrazoles, benzotriazoles, caprolactam, thiocaprolactam, and p-nitro-aniline.
me oximes are aldoximes or ketoximes of the formula H0-N=C
~R"
whereln R' is an alkyl radical containing 1 to about 8 carbon atoms, a cycloalkyl radical containing 4 to 8 carbon atoms, an aryl radical containing 6 to about 12 carbon atoms, or where R' and R", together with the carbon atom, form a carbon ring of 4 to 8 carbon atoms, and R" iæ hydrogen or the same as R'. Examples of the oximes are acetoxime, methylethyl , i ketoxime, methylpropyl ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclohexanone oxime, benzophenone oxime, benzoaldoxime, and the like.
-.:
: .
- 12 - ~
Pyrazole and 1 to 4 carbon atom alkyl substituents thereo~ can be employed. Examples are pyrazole, 3-methyl pyrazole, 3,5-dimethyl pyrazole, and the like.
The benzotriazoles are benzotriazole and 1 to 4 carbon atom alkyl, halogen, and nitro substituents thereof.
Examples of the benzotriazoles are benzotriazole, 5-methyl-benzotriazole, 6-ethylbenzotriazole, 5-chlorobenzotriazole, 5-nitrobenzotriazole, and the like.
The blocking agents are employed on about a 1 to 1 mole basis of isocyanate to agent. The reaction temperature is from about 30C. to about 110C. Reaction time is from about 1 hour to about 15 hours. Suitable solvents for the reaction are aromatic hydrocarbon solvents such as benzene and toluene.
The ethylenically unsaturated blocked aromatic diisocyanates can be polymerized using emulsion (latex), suspension, solution~ and bulk techniques known to those skilled in the art. The polymerization can be performed as a batch reaction~ or one or more ingredients can be propor-tioned during the run. Temperature of polymerization ranges from about -lO~C. to about 100C., whereas a more preferred range is from about 5C. to about 80C.
The polymerization is initiated by free-radical generating agents. Examples o~ such agents are organic peroxides and hydroperoxides such as benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, paramethane hydroperoxide, and the like, used alone or with redox systems; dlazo compounds such as azobisisobutyronitrile, and the like; persulfate salts such as sodium, potassium, and ammonium persulfate, used alone ~ .
1~4i~0~
or with redox systems, and the use of ultraviolet light with photo-sensitive agents such as benzophenone, triphenylphosphine, organic diazos, and the like.
Typical emulsion polymerization ingredients would include a persulfate salt or organic peroxide and uqually a redox system, water adjusted to a desired pH with acids or bases and usually buffered with inorganic salts and either anionic, cationic, or nonionic surface active agents well known to the art. -The polymerization normally is continued until about 90% or more conversion of monomers is obtained. The resulting latex can be coagulated to isolate the polymer. Typical coagulation procedures are salt/acid coagulations, use of polyvalent metal salts such as MgS04, use of alcohols such as methanol and isopropyl alcohol, and freeze agglomeration techniques. The polymer is then usually washed wlth water and dried. -The polymers are comprised of~rom 0.1 percent to 100 percent by weight (i.e., homopolymers) of an ethylenically unsaturated blocked aromatlc diisocyanate(s), as defined, and up to 99.9 percent by weight, and more preferably up to about 70 percent by wei~ht, o~ a copolymerizable vinylidene monomer.
Thls monomer is a vinyl monomer having a terminal vinylidene ;
(CH2=C-) group. Examples o~ these monomers are acrylates and methacrylates such as ethyl acrylate, n-butyl acrylate, octyl acrylate, dodecyl acrylate, methyl methacrylate, phenyl acrylate, cyclohexyl acrylate, and the like; vinyl and allyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, and the like; vinyl ketones such as methyl vinyl ..
ketone? propyl vinyl ketone, and the like; vinyl and allyl ethers such as vinyl methylether, vinyl ethylether, vinyl . . .
isobutylether, allyl methylether, and the like; vinyl aromatics .
1(~41~Ql ;
such as styrene, ~-methylstyrene, p-chlorostyrene, vin~l toluene, vinylnaphthalene, and the likej vinyl nitriles such as acrylonitrile, methacrylonitrile, ~-chloroacrylonitrile, and the like; dienes such as butadiene, isoprene, chloroprene, 2-isopropyl-1,3-butadiene, and the like, ~-monoolefins such as ethylene, propylene, l-butene, l-hexene, and the like;
vinyl halides such as vinyl chloride, vinyl fluoride, vinyl-idene chloride, and the like; and divinyls such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, and the like. In addition, because the isocyanate is blocked, so-called reactive monomers can be copolymerized with the acrylates and unsaturated lsocyanate. Examples of these monomers are vinyl carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, 2-hexanoic acid, and the like, vin~l amides such as acrylamide, methacrylamide, N-methyl methacrylamide, dlacetone acrylamide, and the like; hydroxyl-containing vinyl monomers such as allyl alcohol, vinyl benzyl alcohol, ~- ;
hydroxyethyl acrylate, ~-hydroxypropyl acrylate, 4-hydroxy-butyl acrylate, ~-hydroxyethyl methacrylate, N-methylol acrylamide, and the like.
The polymers are high molecular welght solids having dllute solution viscosities (DSV) of over 0.5 measured on a 0.2 gram sample of the polymer in 100 milliliters of solvent at 25C. The polymers are cured at temperatures as low as 80C. and can be cured under acidic, neutral, or basic pH
conditions.
, . .
The polymers can be admixed with cure ingredients and compounding ingredients using two-roll mills, internal mixers ; such as Banburys and extruders, and like equipment.
~ The polymers, as isolated solid rubbers, can be - cured to prepare useful vulcanizates. Compounding ingredients well known to the art can be used, such as fillers, oils and ~ 15 -.,.: . . - - ~
~ 041~0iL
plasticizers, antioxidants, and the like. Standard mixing and cure techniques are employed. Upon heating the polymer, the blocking agent is released. Hydroxyl, carboxyl, and amine containing materials are used as curing agents. For example, glycols, polyols, polyalkylene amines, hydroxyl and carboxyl containing polyesters and polyethers, hydroxyl, carboxyl, and amine terminated vinylidene polymers, etc., and water itself, are all known and suggested reactants for iso-cyanate-containing materials. If the interpolymer itself contains hydroxyl, carboxyl, or amine groups, the polymer can be considered self-curing. Upon heating, the isocyanate is released and the polymer can undergo intra- and inter-molecular crosslinking.
The polymers do not have to be isolated, but can be readily stored in latex or solution form. The novel polymers have excellent stability in latex form. In non-woven binder applications, the polymers are conveniently used as latexes or solutions to coat or impregnate the fibers. Fillers, extenders, and other ingredients such as stabilizing agents, thickeners, antioxidants, and the like, are readily admixed with the latexes or solutions prior to u~e.
In non-woven flber binder applications, the ethylen-ically unsaturated bl~ked aromatic diisocyanates are preferably copolymerlzed with an acryiate monomer. The interpolymer com-prises from about 0.5 percent to about 50 percent by weightof the diisocyanate(s) as defined, and from about 50 percent to about 99.5 percent by weight o~ an acrylate monomer(s).
More preferably, the interpolymer contains from about 1 percent to about 30 percent by weight of the diisocyanate, from about 70 percent to about 99 percent by weight of an acrylate monomer, and up to 20 percent by weight of another copol~merizable .. .: .. ..
vinylidene monomer, all present as interpolymerized units.
.
~U4~
The acrylate monomer has the formula CH2=C- C~Ra wherein R is H, -CH3 or -C2H5~ and Ra is an alkyl radical containing 1 to about 24 carbon atoms, an alkoxyalkyl or alkylthioalkyl radical containing a total of 2 to about 12 carbon atoms, or a cyanoalkyl radical containing 2 to about 12 carbon atoms total. The alkyl structure can be linear or branched Examples of the acrylates are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl ~
acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, ~ -2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-tetradecyl acrylate, n-octadecyl acrylate, n-eicosyl acrylate, and the like, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, n-octadecyl meth-acrylate, ethyl ethacrylate, n-butyl ethacrylate, and the like, methoxymethyl acrylate, methyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl .
acrylate, methoxyethyl methacrylate, methylthioethylacrylate~
hexylthioethyl acrylate, and the like; and a and ~-cyanoethyl acrylate, a, ~, and ~-cyanopropyl acrylate, cyanobutyl acrylate, cyanohexyl acrylate, cyanooctyl acrylate, cyanoethyl meth-; acrylate, and the like. O~ten mixtures of two or more monomers ~ and/or types o~ acrylate monomers are employed.
-~ 25 More preferably, the interpolymer contains from 70 percent to about 99 percent by weight o~ an acrylate monomer(s) whereln Ra is an alkyl radical containing 1 to about 18 carbon atoms or an alkoxyal~yl radical containing 2 to about 8 carbon atoms. Examples of the more preferred monomers are methyl acrylate, ethyl Icrylate, n-propyl acrylate, isopropyl acrylate, ~ n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl ;~ _ 17 acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, methoxyethyl acrylate, ethoxy-ethyl acrylate, methoxypropyl acrylate, ethoxypropyl acrylate, and the like. Both an alkyl acrylate and an alkoxyalkyl acrylate can be used. Especially good results are obtained when employing ethyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and/or methoxyethyl acrylate.
The interpolymers are applied to the non-woven fibers using dip coating, knife edge coating, roller coating, soaking, spray coating, and like known techniques. Cure conditions depend in part upon the specific blocking agent and aromatic diisocyanate used to prepare the monomer. However, temperatures from about 80C. to about 150C. and more preferably from about 100C. to about 125DC. are usually employed. Cure times range from about 3 minutes to about 30 minutes. An excellent cure is readily obtained at 100C. in about 3 minutes at an acidic, neutral or basic pH.
Examples o~ non-woven fibers are papers such as Kraft paper, crepe paper, and the like, rag fibers, cotton, wool, regenerated cellulose, glass fiber, asbestos, and synthetic fibers such as polyesters~ and the like. In addition to binding fibers to impart tensile strength, edge tear strength, and the like, the lnterpolymers are also use~ul as pigment and filler binders and as fabric adhesives.
The polymers can be copolymers of the essential blocked diisocyanate with acrylate monomers and from about ~ .....
0.5 percent to about 10 percent by weight of a hydroxyl, carboxyl, amlne or amide containing monomer. ~fter applying such an interpolymer to a non-woven substrate and heating it~
the blockingagent is released and the free isocyanate cross-links through these reactive groups to cure the polymer. -However, if the polymer does not have these groups present thereon, compounds containing the groups can be readily added to the latex or solution prior to use. These compounds are crosslinking agents, and include aliphatic and phenolic diols and polyols, diamines and polyamines~ di- and polymercaptans, di- and polycarboxylic acids, and polymeric materials such as polyether polyols, polyester polyols, polyester amides, poly-ether amides~ and the like. Examples o~ crosslinking agents are alkylenediols such as 1,4-butanediol, 1,6-hexanediol, 4-methyl-1,4-pentanediol, l,10-decanediol, and the like; ali-cyclic diols such as 1,4-cyclohexanediol, 2-hydroxymethyl-cyclohexanol, and the like; phenolic diols such as p hydroxy-benzyl alcohol, hydroquinone, 2,2'-dihydroxydiphenyl, methylene-bisphenol, p,p'-isopropylidene bisphenol, and the like; polyols such as 1,3,5-pentanetriol, 1,3,5-trishydroxybenzene, glycerol, sorbital, and the like; alkylenediamines such as ethylene-diamine, 1,2-butylenediamine, 2-methyl-1,4-diaminobutane, hexamethylenediamine, decamethylenediamine, dodecamethylene-diamine, and the like; alicyclic diamines such as 1,4-diamino-cyclohexane, 1,4-diaminoethylcyclohexane, and the like; aro-matic diamines such as m-phenylenediamine, m-xylylenediamine, 3,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, p,p'-bis-aminomethyl diphenylmethane, and the like, heterocyclic dl-amines such as piperazine, aminoethylpiperazineg and the like;
polyamines such as diethylenetriamine, triethylenetetraamine, and the like; and alkanolamines such as tris(hydroxyethyl) amine, bisthydroxyethyl)methylamine, tris(hydroxypropyl)amlne, l-amino-2-hydroxypropane, l-aminomethylcyclohexanol, m-amino-phenol, 2-amino-6-hydroxypyridine, and the like. The more pre~erred crosslinking agents are the alkylenediols, the alk~lenediamines, and the alkanolamines.
The crosslinking agent can be added directly to the latex (or solutionj. It can be dissolved in a solvent such ~(~4~L~Q~
as chloroform or trichloroethylene, or suspended in water using an emulsifying agent, and then added to the latex or solution. No reaction takes place until the blocking agent is released in the cure process. The crosslinking agents are used on about a mole to mole basis of isocyanate to hydroxy, amino, etc., group. Higher levels may be used, but it is not necessary for obtaining fast strong cures.
Of course, water alone can act as a crosslinking agent for the polymers. In the presence of water, the blocked diisocyanate can react to form an amine structure which can then further react with another blocked diisocyanate group to crosslink the polymer. The water can be added to the polymer, or it can be present as residual water in the polymer or saturated non-woven. Atmospheric moisture can also act to ; -crosslink the polymers.
As the novel interpolymers have particular utility as binders for nonwoven fibers, testing was directed to evaluation of the interpolymers in latex form as paper saturants. Actual testing included original and wet tensile strength, using an Instron tensile tester at a pull rate of 12 inches per minute. Wet tensile followed TAPPI procedure T465-m44 (specimens soaked in water for 16 hours before teGting).
The following examples serve to more fully illustrate the invention. .
EXAMPLE I
A series o~ ethylenically unsaturated blocked aro-matic diisocyanates was prepared. The general reaction scheme is to first react a mole of a hydroxyl-containing vinylidene monomer with about two moles of an aromatic diisocyanate, and secondly, react the intermediate product with about 1.1 mole of a defined blocking agent per mole of the intermediate.
. Preparation of 4-(0-methacryloyloxyethyl)-.
1~4~
urethanotolyl(2-carbamoyl)-1-tolyltriazole. The synthesis consists o~ a two-step reaction. Toluene, 1080 grams and 2,4- -toluene diisocyanate~ 1160 grams (6.66 moles), were put into a reactor vessel equipped for stirring and temperature control.
The vessel was then flushed with nitrogen ~as and the inter-mediate product reaction conducted under nitrogen gas. The mix was heated to 60C. while stirring, and 433 grams (3.33 moles) of ~-hydroxyethylmethacrylate slowly added over 5.5 hours. Temperature o~ the mixture rose to 65~C. and was con-trolled there throughout the addition. The mixture was thenstirred for one hour. Total reaction time was about 7 hours.
The reactor mixture (a solution)was cooled to 5C.
and allowed to stand ~or about 16 hours. White crystals formed in the solution. me mixture was then cooled to -30C. and the crystals filtered out and washed with hexane. The inter-mediate product was dried to yield 754 grams o~ a white crystalline solld having a melting point of 71-72C. Analyzed ~or isocyanate content and for unsaturation, the intermediate product proved to be about 99% pure. The yield was 74~ by 20 ~ ~ weight based on the theoretical weight as measured on the hydroxy compound.
The intermediate product (i.e., the ~-hydroxyethyl-methacrylate/2,4-toluenediisocyanate reaction product), 22.3 .
grams (0.0735 mole) was dissolved in 350 milliliters o~
toluene at about 30C. and the solution placed into a reactor vessel., Tolyltriazole, 10.75 grams (o.o808 mole) was dissolved in 50 milliliters of toluene at about 30C. and the solution then~added to the reactor vessel. The mixture was stirred for 3~hours at 30~C. and then at 50C. for 0.5 hour. A white 3~ precipltate forms during the stirring time. Total reaction time is about 4 hours. -- The reaction mixture was cooled to 0C. and the white ~ ~ .
.
~ ~ .
~(~4~
precipitate isolated by filtration. The product was washed with acetonitrile and dried at 25C. under a vacuum to yield 25.6 grams of a crystalline solid having a melting point of 132-133.5C. The yield was 80~ based on the amount of inter-mediate product used. Analysis by unsaturation showed theproduct to be about 99% pure. The product has the structure O N=N~
CH3 O O NH-C-N~
CH2=C - COCH2CH2-OC-NH ~ CH3 ~
B. Preparation of 4-(0-mPthacryloyloxyethyl)ure-thanotolyl(2-carbamoyl)-2-butanone oxime. The intermediate -product prepared above was employed.
Toluene, 2686 milllliters, and 517 grams (1.7 moles) of the intermediate product were placed in a reactor vessel and stirred. Methylethyl ketoxime, 152 grams (1.74 moles) was dissolved in 260 milliliters of toluene and the solution ~ `
added to the reactor vessel slowly over a 1.5 hour period.
Temperature of the reaction was kept at 28-290C. The mixture was then stirred for 16 hours at about 25C., followed by cooling to -30C. A white preclpltate formed whlch was flltered out and dried to yleld 494 grams of product (a 74%
yield). The crystalline product has a melting point of 80.50-820C., and analyzed by unsaturation to be about 98% pure.
The theoretlcal nltrogen content of the product is 10.7~ by weight and the analyzed nitrogen content was measured to be 10.6~ by weight. The product has the structure .
,~ C2H5 ~ ,CH3 1t ~ NH-CON=C
CH2-C - COCH2CH2-OC-NH ~ CH3 CH3 :
Ql C. Following the procedure given in B above, the ~ollowing compound was prepared by reacting the intermediate product with acetoxime:
" ,CH3 CH O O NH-CON=C
~ 3 ~ r--<
CH2~C - COCH2CH2-OC-NH ~ 3 H3 D to E. Following the procedure given in B, the inter-mediate product was reacted with meth~lisobutyloxime and di-methylpyrazole, respectively, to yield:
,0, Cl H2 . .:
t~ It CH2=C COCH2CH2-OC-NH ~ CH3 CH3 melting point o~ 75-79.5C., and O / ~ H3 CH3 ,0, ,, ~ NH-C-N
CH2-C COCH2CH2-OC-NH ~ CH3 CH3 melting point of 109-110.5C.
F. Followlng the procedure glven in A above~ ~-hydroxyethyl acrylate and 2,4-toluene dlisocyanate were reacted together to form an intermedlate product which was then reacted with methylethyl ketoxime. The product is ~; O ,C2H5 ', '.
H O O~ ~ H-CON=C
CH2-C-COCH2CH2-OC-NH ~ CH3 CH3 melting point of 1~08-113C. The compound was tested to be 95% pure using a standard isocyanate analysis test.
G. Following the procedure given in A æbove, ~
. ' ' "
- 23 - ~
Q~
p-vinylbenzyl alcohol was reacted with 2,4-toluene diisocyanate, followed by reaction with methylethyl ketoxime. The product is . ~ .
o C2H5 H O NE-CON=C
CH2 C ~ CH2-OC-NE ~ CH3 CH3 melting point of 79.5~-83C.
FXAMYLE II
The ethylenically unsaturated blocked aromatic di-isocyanate prepared ln Example I in procedure B was inter- ~ - :
polymerized with a vinylidene terminated monomer, using an emulsion polymerization system. The recipe is as follows: - i Ethyl acrylate grams 94.1 `
Diisocyanate B~ grams 5.9 Water, milliliters 175 Sodium lauryl sulfonate 30 millilitersb N~halene sbulfonate, 9 milliliters Sodium hydrosulfite, 8.3 , millilitersC, Sodium formaldehyde sulfoxalate, 10 millilitersd Sodium salt of ethylene diamine 8.3 tetraacetic acid and sodium gluconate, milliliterse p-methane hy~roperoxide, 0.2 millilitersl O
CH3 O O H-coN=c~ 2E5 a CH2=C - COCH2CH2-OC-NE ~ CH3 CH3 b 10% by weight in water ;
c o,5% by weight in water d 1.0% by weight in water .
e 0.24 and 0.13 grams in 100 milliliters of water f 50~ by weight The dlisocyanate was dissolved in the ethyl acrylate, and the solution admixed with the water, sodium lauryl sulfonate, ".. '.
- ' ~:, - .
.. . ... .. . ~ . ~ , ~,. ., , , .. - .
sodium hydrosulfite, and naphthalene sulfonate. 17 milliliters of the mixture was placed in a reactor vessel followed by the sodium formaldehyde sulfoxalate, sodium salt of ethylene diamine tetraacetic acid and sodium glyconate, and p-menthane hydroperoxide~ An immediate exotherm occurred and temperature of the reaction was controlled at 27~3C. Using a stirred dropping funnel, the remaining mixture was slowly added to the reactor vessel over a 1 hour period. After the addition was complete, the reactor mix stood for 16 hours. Total conversion of monomers to polymer was 96%, based on the total solids of the mix.
EXAMPLE III
Interpolymers of ethylenically unsaturated blocked aromatic diisocyanates (as prepared in Example I) and ethyl acrylate, were prepared following the procedure of Example II.
The ~ollowing polymeric samples were prepared and evaluated in thelr latex form.
.
' :
N 1~ C ~ m ~i~ V- ~- V U- ~- U V--V--V--V
o= V ~ o- V ,~ O- V ~ U o ~I z Oo _ V o _ V o = V o- o , ~ , rlU V V V ' ' ~v~ ~ ~ . u o- VO Ot V o C~ O- U . .
N ~ P l : :~` .3 ,,~
. ~ .~ ` ` .
.. . ~ . .
I ~ 11 14~
æ ~N ~ N
o~ o ~d 5~ ~ O O = C~
a) ~; 1o = ~ ~ , ~ ~ -I P~ ~ V a) ~PJ~ . ~
o ~
o æ
p~ o= O ~ o ~ .
P~
~ ~ 1 o Or ~
, ~ , , o . .:
: ' -o ", . ~ ,..
C) C) . ~, . . .
o~
:
-- h C) ~ ' '., .
~ ' ,, .
' ' ' ' '- ' ~, ' ' .
' ' .
~ . , .. .
The latex samples were used at a total solids content ...... .. .
of about 20% by weight. The non-woven ~iber employed was saturatlon grade, bleached Kraft paper of 11 mils thickness.
8 inch by 1 inch strips of the paper were soaked in each sample latex. Solids pickup was about 50~ by weight for each test strip. The strips were then dried at room temperature followed by curing at selected temperatures and times. When an added crosslinker was employed, it was dissolved in or added to the latex as a solution or suspension prior to soaking I0 the paper strips.
Evaluation consisted of wet tensile strength testing following Tappi procedure T465-m 44. The impregnated paper strips were soaked overnight in water and then pulled on an . . , :, .
Instron tensile tester at a ~aw speed of 12 inches per minute.
Test strip samples were run in triplicate and the arithmetric average reported.
The crosslinker employed in this series o~ experi-ments i8 either residual water (i.e., no crosslinking agent was added~ or triethanol amine. When triethanol amine was used, it was simply dissolved in the latex, prior to soaking the samples? at none, one, or two mole equivalent~ of cross-linker per mole equivalent o~ isocyanate group on the polymer.
The data obtained is listed in the ~ollowing table.
Wet Tensile Strength Latex Part~ by Wt. of 3 Mlnute Cure At Sample Triethanol aminea 100C. 125C. 150C.
none 18 20 20 0.75 21 20 21 1.50 22 20 22 3 B none 20 22 23 1.~0 22 24 25 C none 15 21 27 0.?5 18 23 29 , . .
D none 20 22 21 3~ - 0.75 20 21 21 , f l~ L101 Wet Tensile Strength Latex Parts by Wt. of 3 Minute Cure At Sample Triethanol Aminea 100C. 125C. 150C.
E none 22 23 24 1.50 20 23 22 F none 21 22 23 0.75 21 24 24 G none 19 23 22 0.75 20 23 24 aParts by weight per 100 parts by weight of polymer in the latex The data shows that excellent wet tensile strength is exhibited by all of the æamples. The paper strip, without -. .
being impregnated by the novel polymers, has a wet tensile ~-strength of about 0.5 psi. The Example shows the excellent -results obtained using the novel polymers in latex form as non-woven fiber binders. me strength obtained is as good as or better than results obtained using commercial latexes, especially at low cure temperatures. For comparison, a commercial acrylic latex would exhibit, cured at lOO~C. using no crosslinker, a wet tensile strength of about 4 psi at a basic pH to a high of about 16 psi at an acid pH.
EXAMPLE IV
Following up Example III in more detail, sample latex A was used to prepare wet tensile ~amples at various pH's of the latex. Using 0.90 parts by weight of 1,6-hexane-dlol as a crosslinker, after cure at 100C. for 3 minutes, the wet tensile strength values were: pH of 5, 20 p8i, pH of 7, 20 psi, and pH of 9, 19 psl. Repeating the test using 0.75 ~ parts by weight of triethanol amine as the crosslinker, the values were: pH of 5, 21 psi; pH of 7, 21 psi; and pH of 9, 21 psi. In contrast, two commercial acrylic latexes were also evaluated as to their ability to impart wet tensile strength over a range of pH values with the following results: p~I of 5, .
, , ., - - . :
- 29 ~
~.L~Ql 11 psi and 6 psi, respectively; pH of 7, 8 psi and 6 psi~
respectively; and pH of 9, 4 psi and 4 psi, respectively.
The exam~le shows that not only do the polymers of the invention impart greater wet tensile strength to non-wovens than known commercial latexes, compared at a 100C. cure temperature, but the novel polymers are also not sensitive to pH as the commercial acrylic latexes are. At a cure temperature :
of 80C., a test sample using the novel polymer prepared as sample B had a wet tensile strength of 14 psi (cured 3 minutes). ~
The difference between the novel polymers of the invention - ~, and the commercial latexes diminishes as the temperature of cure increases and the pH of cure decreases. However, fast :
cures at low temperatures over a range of pH conditions is highly desirable.
. . .
EXAMP~E V
The ultimate tensile strength and wet tensile strength of a bound non-woven fiber is a function of both the polymeric binder and the crosslinking agent employed. Of the known crosslinking agents, the use of alcoholic amines is preferred with the novel polymers of this invention. Using the polymer latex prepared as sample A in Example III, and following the procedure given in Example III, various cross-linking agents were evaluated at one equivalent weight as to their abillty to develop rapid and high strength cures.
. .
Ql ~ ~
.: - . . .
~, o ~C--O ~ ~-.l C~J N N cu c~l ~ ~1 ":':
o u~ C~ N C~ N N ~1 ~1 rl . .. :
~ O ~ ~ ~ ~1 ~1 ~ CU ~ "
O ~1 ~I N ~ C~J C~ ~I h ;-a~ ~1 . ~ .. .
E~ h ol ~0 o ,I N o ~3: X) l ~1 ~1 ~ ~I N c~
o : :
~ ~ o bD "' ~`"''' . .
. . o 0~ 1~ 0 00 0 ~ rl h . .... , . ~q o ~R O ~ O O O
a~ . ~
P~ ~ o : . ., o O ~ h . ~ ~ ~ ~r O O r~
~: ~E c h r~ O ~r ~:! r ~ a) ~q .
O ~rl ~ ~ Ci ~r~ ~C
O ~ r ~ ~3 a ~ ~:! O r~ a) r~ cq h,r-l - ~d c~ ~ O ~1~ n~ ~ a 5 . a) ~ c~ o o rl ~ 5'~ ~ ~ ~ O ~ ~q 5'~ ::
~0 O . I O (1~ ~ 5 N ~Q Ul t~ h - O 5~0 r1~ ~ r~ rl h O ~ ~ h ~rl C) ~ r~
C,) ~z; r-l r~ ) r~ cB ~ C) .~ ~ - : '' - " ' ' r~
r~ 0 ~ ,..... ..
:. , ; . .:
:: :
` ~: . ~: :
::
EXAMPLE VI
The polymers of the present invention present a unique balance between rapid cure at low temperatures (evidencing quick, efficient release of the blocking agent) and stability, especially to hydrolysis in the presence of water. This unique balance is struck by the use of both the aromatic dilsocyanate and the specified blocking agents in the preparation of the novel ethylenically unsaturated blocked aromatic isocyanates. The following data shows that the polymers of the invention have good stability to hydrolysis.
Polymer latex sample B prepared in Example III is employed. ~
Testing consisted of wet tensile strength before and after ;
aging at room temperature.
Wet Tensile Sample B Strength, psi Time Aged Test Strip Cl~rginal Aged (days) ~;
.:
Cured ~i 3' at 100C. 20 14 50 -;
3' at 125C. 22 19 50 3' at 150C. 23 19 50 Aged in presence 0~ 0.75 parts by wt. of triethanol amine Cured 3' at 22 19 50 100C. 22 17 100 3o EXAMPLE VII
Expanding on Example VI, other polymers o~ this invention were prepared following the procedures given in Examples I and II, and evaluàted as to their stability to hydrolysis and their ability to impart wet tensile strength to non-woven flbers. Original and aged wet tensile strength ~ . - .
of impregnated non-woven paper was determined following the ~ - 32 -1~4~ Q~ :
procedure in Example III. Results are reported in the following tables.
, ~, .
: . .
. ', ' ~- :
- '' ' .' ";
.
. ::
, . . .
.,: , ::
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~ _ 33 _ ~ .
: : ;
Ql ~ ~, .
V V V V V V V ~ ~
~ , ~ v ~ v ~ V- o V ~ V- o ~ o ~~ ~ X .. : ' ~3 C) o= ov o- V o ~ o , o ~ ~ V V
~v~ ~ v~
. o o o o vl ~ ~
C~- V , V- V
V- V ..
.
V C~ V
. ..
,, , .: :.
. ,~
~ .o~ ~o h 00 ~ :
a~
1:4 ., ', ' ~ , .~
'' a) :
~1 . ~j :' "' U~ ,:
P:~ H ~
O : :
: "; ' , .
' ' ,', . ~:
- . - 34 -. .- . : - ::-v ~ ~ ~ ~ o ~
~ v- v v- v- v o o-v ~
l ~ o ~ ~ o q o = ~ ~ :
~d~ ~
~ o- v l l ~ :
c) o o- v o- v o l o o ~
V ~ ~ ~:
~ p:~ P:~
o v v o- v o o ~
I o I o p~
v v o ~ :
~ ~ .. .
: ~ . ll :~ ~ ~
~ o ~ :
~ . tq ~ : p~
~O O o o F~ h ~, h P~
~ bD ~
O ~ 1~1 ¢
~ ;~
~ .
O : .: ' ' P~ . . ~
. ' :: , .~ .
:.
' ~
- 35 ~
- ; , .. . . ~ ~ . , ...... .: ~ . . , . ~ .. . . . .. . . . .. . . .
The polymers above, in latex form, were used to impregnate saturation grade, bleached Kraft paper (11 mils thick) ~ollowing the procedure in Example III. The test sample strips were then evaluated for their original wet tensile strength. Following Example VI, after allowing the polymer latex samples to age, test sample strips were again prepared and the wet tensile strength measured. Results are reported below.
Wet Tens~le Average Latex Stren~th , psi % Decrease -Sample Original Aged ays Per Day B 20 12 100 0.40 H 20 17 45 0.33 14 100 0.30 J 20 17 30 0.50 0.42 K 162 11 34 0.92 6~ 0.45 M 223 15 5 o.64 ' 1 Cured 3 minutes at 100C., no crosslinker added 2 At 15th day 3 At 70th day The data shows that the polymers of the present invention, samples B and H to M, prepared using the novel ethylenlcally unsaturated blocked aromatic diisocyanates, im~art good wet tensile strength to non-woven flbers, and have unexpectedly good stability to hydrolysis when stored as a latex. If a crosslinker and/or higher cure temperatures are employed with the novel polymers, higher original and aged wet tensile strengths are obtained. For example, sample I, which showed the least stability, can be cured at 150C. using 0.75 parts o~ triethanolamine (after 47 days of aglng) to yield , - ~
~ - 36 -.~, ' :. ..
a wet tensile strength of 19 psi.
EXAMPLE VIII
If, instead of reacting the hydroxyl-containing monomer with the aromatic diisocyanate, the blocking agent is first reacted with the aromatic diisocyanate, different variations in the structure of the ethylenically unsaturated blocked aromatic diisocyanate can be prepared. For example, in Example I, procedure A, the following diisocyanate was prepared:
.. N--N
CH3 0 0 ~ H-C-~
CH2=C - COCH2CH2-OC-NH ~ 3 ~
When the methylbenzotriazole was first reacted with the 2,4-toluene diisocyanate, followed by reaction with the ~-hydroxy-ethyl acrylate, the structure is:
CH3 0 o " "
CH2~C - COCH~CH2-OC-N ~ " /N= N
CH3 ~ NH-C-N
~ CH3 me diisocyanate prepared by the reverse addition ;l ;
o~ materials can be easily polymerized with vinylidene-termin-ated monomers via emulsion techniques, and is useful in latex iorm as a binder ~or non-woven ~ibers. The following data shows this fact.
Latex Wet Tensile Strength~ psib ::
pa 15 16 19 22 :' .
a 96% by weight ethyl acrylate,
4% by weight diisocyanate b 3 minute cure The~polymer was prepared following the procedure in .: .
_ 37 _ ~--, Example II. Testing followed the procedure in Example III.
Use of an added crosslinker raises the value of the we~
tensile strength.
EXAMP~E IX
Following procedures in previous Examples, the diiso-cyanates made in Example I as C and E were interpolymerized with ethyl acrylate and ~-hydroxyethyl methacrylate. The polymers were evaluated in latex form as binders for non-woven paper. Data is as follows:
Latex Wet Tensile Stren th psi Sample lOODC. 12~C. ~ .
Qa 17 18 18 Rb 15 21 24 a 93.8% ethyl acrylate 1.5% ~-hydroxy-ethyl methacrylate, ~.7% diisocyanateE
b 95.6% ethyl acrylate, 1.3~ ~-hydroxy-ethyl methacrylate, 3.1% diisocyanate C
EXAMPLE X
Diisocyanate sample B from Example I was lnterpolymer-ized~with ethyl acrylate via an emulsion polymerization process.
me recipe was:
Ethyl acrylate grams 20.4 Dllsocyanate Ba, grams 12.9 Water~ milllliter~ 68 Sodium laury~ sul~onate, 10 millilitersD
~mmonium persulfate~ grams 6.5 a CH2=C C0-CH2CH2-OC-NH ~ CH3 ,C2H5 NH-C0-N~C
. . " ~ . .
~ b 10~ by weight ln water 3o me ethyl acrylate, diisocyanate B, sodium lauryl sulfate solution, and 4 millillters of water were mixed ~together in a stirred dropping ~unnel. 2 milliliters of the ;; .' . ~ ,,, ~ _ 38 -... . . .
a~ . .
mixture was then placed into the reactor vessel with 62 milli-liters of water and the ammonium persulfate (dissolved in 2 milliliters of water). The temperature was raised to 50C.
and held at 55~ 2C. throughout the run. The remaining monomer mixture was added over a 20 minute period. Total reaction time was 1.5 hours. Percent conversion of monomers to polymer was 96% based on total solids. The example demon-strates that interpolymers containing high weight percents of the ethylenically unsaturated blocked aromatic diisocyanates of this invention can be readily prepared. In this example, the interpolymer composition was about 61% by weight ethyl acrylate and about 39% by weight of the specific diisocyanate. ;;
: '; ,' ' `-I . . :, ! . '. ' ..
'~
~,' ~"' .' ;''.
. .
" ~ ." ' ' ~ ~ " ' , ' ' . ' ' ' .' "
, ~ ' ', ' ~. ,''-_ 39 -: - . .
. - ~ - , .
_ 37 _ ~--, Example II. Testing followed the procedure in Example III.
Use of an added crosslinker raises the value of the we~
tensile strength.
EXAMP~E IX
Following procedures in previous Examples, the diiso-cyanates made in Example I as C and E were interpolymerized with ethyl acrylate and ~-hydroxyethyl methacrylate. The polymers were evaluated in latex form as binders for non-woven paper. Data is as follows:
Latex Wet Tensile Stren th psi Sample lOODC. 12~C. ~ .
Qa 17 18 18 Rb 15 21 24 a 93.8% ethyl acrylate 1.5% ~-hydroxy-ethyl methacrylate, ~.7% diisocyanateE
b 95.6% ethyl acrylate, 1.3~ ~-hydroxy-ethyl methacrylate, 3.1% diisocyanate C
EXAMPLE X
Diisocyanate sample B from Example I was lnterpolymer-ized~with ethyl acrylate via an emulsion polymerization process.
me recipe was:
Ethyl acrylate grams 20.4 Dllsocyanate Ba, grams 12.9 Water~ milllliter~ 68 Sodium laury~ sul~onate, 10 millilitersD
~mmonium persulfate~ grams 6.5 a CH2=C C0-CH2CH2-OC-NH ~ CH3 ,C2H5 NH-C0-N~C
. . " ~ . .
~ b 10~ by weight ln water 3o me ethyl acrylate, diisocyanate B, sodium lauryl sulfate solution, and 4 millillters of water were mixed ~together in a stirred dropping ~unnel. 2 milliliters of the ;; .' . ~ ,,, ~ _ 38 -... . . .
a~ . .
mixture was then placed into the reactor vessel with 62 milli-liters of water and the ammonium persulfate (dissolved in 2 milliliters of water). The temperature was raised to 50C.
and held at 55~ 2C. throughout the run. The remaining monomer mixture was added over a 20 minute period. Total reaction time was 1.5 hours. Percent conversion of monomers to polymer was 96% based on total solids. The example demon-strates that interpolymers containing high weight percents of the ethylenically unsaturated blocked aromatic diisocyanates of this invention can be readily prepared. In this example, the interpolymer composition was about 61% by weight ethyl acrylate and about 39% by weight of the specific diisocyanate. ;;
: '; ,' ' `-I . . :, ! . '. ' ..
'~
~,' ~"' .' ;''.
. .
" ~ ." ' ' ~ ~ " ' , ' ' . ' ' ' .' "
, ~ ' ', ' ~. ,''-_ 39 -: - . .
. - ~ - , .
Claims (10)
1. An ethylenically unsaturated blocked aromatic diisocyanate of the formula wherein R is hydrogen or a methyl or ethyl radical; A is a carbonyloxyalkylene radical containing 2 to about 8 carbon atoms or an aralkylene radical containing 7 to about 12 carbon atoms; B is a bivalent aromatic radical selected from the group consisting of arylene, napthalene, and the structure where R is defined as above; Y is O, S, or ; n = O
to 3; and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime selected from the group consisting of acetoxime, methylethyl ketoxime, methylpropyl ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclohexanone oxime, benzophenone oxime, benzoal-toxime; benzimidazole; a pyrazole; a pyrazole selected from the group consisting of pyrazole, 3-methyl pyrazole, 3,5-dimethyl pyrazone; and a benzotriazole selected from the group consisting of benzotriazole, 5-methylbenzotriazole, 6-othylbenzotriazole, 5-chlorobenzotriazole and 5-nitrobenzotriazole.
to 3; and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime selected from the group consisting of acetoxime, methylethyl ketoxime, methylpropyl ketoxime, methylisobutyl ketoxime, ethylhexyl ketoxime, cyclohexanone oxime, benzophenone oxime, benzoal-toxime; benzimidazole; a pyrazole; a pyrazole selected from the group consisting of pyrazole, 3-methyl pyrazole, 3,5-dimethyl pyrazone; and a benzotriazole selected from the group consisting of benzotriazole, 5-methylbenzotriazole, 6-othylbenzotriazole, 5-chlorobenzotriazole and 5-nitrobenzotriazole.
2. An ethylenically unsaturated blocked aromatic diiso-cyanate of claim 1 wherein R is hydrogen or a methyl radical; B
is phenylene, tolylene,naphthalene, or the defined structure where Y is , and n = 0 to 1.
is phenylene, tolylene,naphthalene, or the defined structure where Y is , and n = 0 to 1.
3. A polymer comprising from about 0.1 percent to 100 percent by weight of polymerized units of an ethylenically unsaturated blocked aromatic diisocyanate of the formula wherein R is hydrogen or a methyl or ethyl radical, A is a carbonyloxyalkylene radical containing 2 to about 8 carbon atoms or an aralkylene radical containing 7 to about 12 carbon atoms; B is a bivalent aromatic radical selected from the group consisting of arylene, naphthalene, and the structure where R is defined as above, Y is O, S, or ; n = 0 to 3; and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime, benzimidazole, pyrazole, benzotriazole, caprolactam, thiocaprolactam, or p-nitroaniline, and up to 99.9 percent by weight of polymerized units of a copolymerizable vinylidene monomer.
4. A polymer of Claim 3 where in the ethylenically unsaturated blocked aromatic diisocyanate, R is hydrogen or a methyl radical, B is phenylene, tolylene,naphthalene, or the defined structure wherein Y is , and n = 0 to 1.
5. A polymer of Claim 4 comprising from about 0.5 percent to about 50 percent by weight of an ethylenically unsaturated blocked aromatic diisocyanate and from about 50 percent to about 99.5 percent by weight of an acrylate monomer of the formula where R is hydrogen or a methyl or ethyl radical, and Ra is selected from the group consisting of an alkyl radical containing 1 to about 24 carbon atoms, an alkoxyalkyl or alkylthioalkyl radical containing a total of 2 to about 12 carbon atoms, and a cyanoalkyl radical containing 2 to about 12 carbon atoms.
6. A polymer of Claim 4 comprising from about 1 percent to about 30 percent by weight of an ethylenically unsaturated blocked aromatic diisocyanate, from about 20 per-cent to about 99 percent by weight of an acrylate monomer, and up to 20 percent by weight of another copolymerizable vinylidene monomer.
7. A polymer of Claim 5 wherein Ra is an alkyl radical containing 1 to about 18 carbon atoms or an alkoxy-alkyl radical containing 2 to about 8 carbon atoms.
8. A latex comprising (A) water and (B) a polymer comprising from about 0.1 percent to 100 percent by weight of polymerized units of an ethylenically unsaturated blocked aromatic diisocyanate of the formula wherein R is hydrogen or a methyl or ethyl radical; A is a carbonyloxyalkylene radical containing 2 to about 8 carbon atoms or an aralkylene radical containing 7 to about 12 carbon atoms; B is a bivalent aromatic radical selected from the group consisting of arylene,naphthalene, and the structure where R is defined as above; Y is 0, S, or ; n - 0 to 3; and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime, benzimidazole, pyrazole, benzotriazole, caprolactam, thiocaprolactam, or p-nitroaniline, and up to 99.9 percent by weight of polymerized units of a copolymerizable vinylidene monomer.
9. A latex of Claim 8 wherein (B) is a polymer comprising from about 1 percent to about 30 percent by weight of an ethylenically unsaturated blocked aromatic diisocyanate, from about 20 percent to about 99 percent by weight of an acrylate monomer, and up to 20 percent by weight of another copolymerizable vinylidene monomer.
10. An article comprising (l) a nonwoven fiber coated or impregnated with (2) a polymer comprising from about 0.1 percent to 100 percent by weight of polymerized units of an ethylenically unsaturated blocked aromatic diiso-cyanate of the formula wherein R is hydrogen or a methyl or ethyl radical; A is a carbonyloxyalkylene radical containing 2 to about 8 carbon atoms or an aralkylene radical containing 7 to about 12 carbon atoms; B is a bivalent aromatic radical selected from the group consisting of arylene, naphthalene, and the structure where R is defined as above; Y is 0, S, or , n -0 to 3; and X is the radical fragment remaining after a hydrogen atom is removed from the nitrogen atom of an oxime, benzimidazole,pyrazole, benzotriazole, caprolactam, thiocapro-lactam, or p-nitroaniline, and up to 99.9 percent by weight of polymerized units of a copolymerizable vinylidene monomer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA213,664A CA1041101A (en) | 1974-11-12 | 1974-11-12 | Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereof |
| DE19742454253 DE2454253A1 (en) | 1974-11-12 | 1974-11-15 | Unsatd blocked aromatic diisocyanates - as monomers for fibre-binding latices |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA213,664A CA1041101A (en) | 1974-11-12 | 1974-11-12 | Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereof |
| DE19742454253 DE2454253A1 (en) | 1974-11-12 | 1974-11-15 | Unsatd blocked aromatic diisocyanates - as monomers for fibre-binding latices |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1041101A true CA1041101A (en) | 1978-10-24 |
Family
ID=25667750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA213,664A Expired CA1041101A (en) | 1974-11-12 | 1974-11-12 | Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereof |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1041101A (en) |
| DE (1) | DE2454253A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395892A (en) * | 1992-11-03 | 1995-03-07 | Basf Aktiengesellschaft | Copolymers crosslinking at room temperature |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3345104A1 (en) * | 1983-12-13 | 1985-06-13 | Bayer Ag, 5090 Leverkusen | ARYLAMINE DERIVATIVES POLYMERIZABLE IN UNSATURATED RESINS, THEIR PRODUCTION AND THEIR USE AS A CURING ACCELERATOR |
-
1974
- 1974-11-12 CA CA213,664A patent/CA1041101A/en not_active Expired
- 1974-11-15 DE DE19742454253 patent/DE2454253A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395892A (en) * | 1992-11-03 | 1995-03-07 | Basf Aktiengesellschaft | Copolymers crosslinking at room temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2454253A1 (en) | 1976-05-20 |
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