CA1172797A - Terpolymers of acrylic acid esters, vinyl esters and unsaturated nitriles and their preparation - Google Patents
Terpolymers of acrylic acid esters, vinyl esters and unsaturated nitriles and their preparationInfo
- Publication number
- CA1172797A CA1172797A CA000336720A CA336720A CA1172797A CA 1172797 A CA1172797 A CA 1172797A CA 000336720 A CA000336720 A CA 000336720A CA 336720 A CA336720 A CA 336720A CA 1172797 A CA1172797 A CA 1172797A
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- Prior art keywords
- weight
- acrylic acid
- terpolymers
- parts
- acid esters
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Terpolymers of acrylic acid esters, vinyl esters and unsaturated nitriles and their preparation A b s t r a c t Terpolymers of acrylic acid esters, vinylesters and unsaturated nitriles, which have a hardness difference (Shore A) between 20° C and 70° C of less than 14 points, consist of two phases, the glass transition point of one phase being below 268°K and the vulcanisates of which without after-annealing have an ultimate tensile strength above 9,o MPa, an elongation of above 180%and a compression set below 35 % (70h/150° C).
Le A 19 019
Le A 19 019
Description
t 1 72797 l'he present invention relates to_terpolymers of acrylic acid esters, vinyl estars and unsatur-ated nitriles and to a proces~ for their preparation.
The terpolyme~s can be peroxidically cross-linkcd ~they have a Mooney viscosity of at least 40 (ML-41/100C), and their rulcanisates obtained without after-anneali~g have an ultimate tensile strength above 9.0 MPa with an elongation above 180%anda compression ~et (70 h/
150C) below 35~. The terpolymers also have ahardness difference (Shore A) between 20C and 70C of less than 14 pointY. The terpolymers consist of two phases, and the glass transition point of one phase i9 below 268K.
The copol~merisation of butyl acrylate and vinyl acetate in emulsion or suspension is known. According to our present ~tate of knowledge, these polymers contain two incompatible polymer phases which are characterised by two different glass transition points. One polymer phase consists, according to it~ ~lass ~an~ition point, of pure polyvi~yl acetate.
Such incompatible diphasic synthetic rubber systems are unsuitable for the manufacture of rubber articles because o~ their inadequate elastomeric propertie~. They are usually supplied as lacquers or paper coating compounds in the ~o~m of dispersions, or together with other monomers, as bi~ders or adhesi~e di~persions.
It is also known to produce elastomers which are resistant to heat and swelling by the polymerisation of suitable acrylic acid esters which are cross~linked by the incorporation of a suitable comonomer. These are usually compounds containing an activated chlorine ~ 17279 atom which is su~iciently mobile to bring about a cross-linking reaction between the elastomer chains. Cross-linking mechanisms of this type re~uire so-called a~ter-.annealing ~or most purposes, For many applications, however, the after annealing of vulcanizates is a serious disadvantage and is very expensive~ I~ it is desired to apply cross-linking mechanisms which do not require a~ter-annealing, it is ne.cessary to resort to the known types o~:.~ulcanization such as cross-linking with sulphur or radical cross-linking; the latter may be initiated by pero~ides or by high energy radiation.
Radical cross-linking both o~ homopolymers o~ acrylic acid esters and oi ~polymers o~ di~erent acrylic acid est.er.~.~Qsults in vulcanizates having mechanical properties which are not satis~actory ~or practical purposes. .In particular the. C~mpre~sion set~ . o~ such vulcanizates is too high, so that the products cannot be used in ~ields o~ application where these properties are particularly impor-tant. ~hese vulcanizates wh~h cannot be optimally cross-li~ked have only a moderate resistance to swelling, and their heat resistance is also les~
than desirable~ An improvement c~ , in some cases, be achieved by a~ter annealing but thi~ is an e~pensive process and is impracticable ~or many articles.
It is there~ore an object oi the present invention to provide terpolymers o~ acrylic acid esters, vinyl Le A 19 019 1 172'~7 esters and unsaturated nitriles which do not have the aforementioned disadvantages.
Accordingly, the present invention provides terpolymers of from 60 to 80% by weight of acrylic acid esters, from 12 to 34% by weight of vinyl esters, and from 0.5 to 12% by weight, preferably from 3 to 6% by weight of unsaturated nitriles, the nitriles being present in such a quantity that the sum of com-ponents adds up to 100~.
The following are mentioned as examples of acrylic acid esters: acrylic acid esters having from 2-8 C-atoms in the alcohol components, such as ethyl, propyl, butyl, hexyl and
The terpolyme~s can be peroxidically cross-linkcd ~they have a Mooney viscosity of at least 40 (ML-41/100C), and their rulcanisates obtained without after-anneali~g have an ultimate tensile strength above 9.0 MPa with an elongation above 180%anda compression ~et (70 h/
150C) below 35~. The terpolymers also have ahardness difference (Shore A) between 20C and 70C of less than 14 pointY. The terpolymers consist of two phases, and the glass transition point of one phase i9 below 268K.
The copol~merisation of butyl acrylate and vinyl acetate in emulsion or suspension is known. According to our present ~tate of knowledge, these polymers contain two incompatible polymer phases which are characterised by two different glass transition points. One polymer phase consists, according to it~ ~lass ~an~ition point, of pure polyvi~yl acetate.
Such incompatible diphasic synthetic rubber systems are unsuitable for the manufacture of rubber articles because o~ their inadequate elastomeric propertie~. They are usually supplied as lacquers or paper coating compounds in the ~o~m of dispersions, or together with other monomers, as bi~ders or adhesi~e di~persions.
It is also known to produce elastomers which are resistant to heat and swelling by the polymerisation of suitable acrylic acid esters which are cross~linked by the incorporation of a suitable comonomer. These are usually compounds containing an activated chlorine ~ 17279 atom which is su~iciently mobile to bring about a cross-linking reaction between the elastomer chains. Cross-linking mechanisms of this type re~uire so-called a~ter-.annealing ~or most purposes, For many applications, however, the after annealing of vulcanizates is a serious disadvantage and is very expensive~ I~ it is desired to apply cross-linking mechanisms which do not require a~ter-annealing, it is ne.cessary to resort to the known types o~:.~ulcanization such as cross-linking with sulphur or radical cross-linking; the latter may be initiated by pero~ides or by high energy radiation.
Radical cross-linking both o~ homopolymers o~ acrylic acid esters and oi ~polymers o~ di~erent acrylic acid est.er.~.~Qsults in vulcanizates having mechanical properties which are not satis~actory ~or practical purposes. .In particular the. C~mpre~sion set~ . o~ such vulcanizates is too high, so that the products cannot be used in ~ields o~ application where these properties are particularly impor-tant. ~hese vulcanizates wh~h cannot be optimally cross-li~ked have only a moderate resistance to swelling, and their heat resistance is also les~
than desirable~ An improvement c~ , in some cases, be achieved by a~ter annealing but thi~ is an e~pensive process and is impracticable ~or many articles.
It is there~ore an object oi the present invention to provide terpolymers o~ acrylic acid esters, vinyl Le A 19 019 1 172'~7 esters and unsaturated nitriles which do not have the aforementioned disadvantages.
Accordingly, the present invention provides terpolymers of from 60 to 80% by weight of acrylic acid esters, from 12 to 34% by weight of vinyl esters, and from 0.5 to 12% by weight, preferably from 3 to 6% by weight of unsaturated nitriles, the nitriles being present in such a quantity that the sum of com-ponents adds up to 100~.
The following are mentioned as examples of acrylic acid esters: acrylic acid esters having from 2-8 C-atoms in the alcohol components, such as ethyl, propyl, butyl, hexyl and
2-ethylhexylacrylate, preferably butyl acrylate.
The following are examples of vinyl esters: vinyl esters having from 1 to 4 C-atoms in the acyl chain, such as vinyl acetate, propionate and butyrate, preferably vinyl acetate.
The following are examples of unsaturated nitriles:
Acrylonitrile, which may be substituted by a methyl group or a chlorine atom, such as methacrylonitrile.
The present invention also provides a process for the preparation of the terpolyme.rs, characterised in that from 40 to 75 parts by weig~t of an acrylic acid ester, from 20 to 55 parts by ~eight of a vInyl ester, and from 0.5 to 9 parts by weight of a unsaturated nitr~le are polymerised in aqueous suspension or emulsion in the presence of a monomersoluble and or water-soluble polymerisat~on initiator at temperatures of from 0 to 60C, preferably of from 10 to ~ ~ - 4 -.
50C5 to a conYersion o~ up to 90~, pre~erably o~
up to 80%.
The dispersing and emulsi~ying agents and the polymerisation initiators which may be used are generally known.
E~amples of suitable dispersing agen-ts include carboxymethylcellulose and methylcellulose.
~ he ~ollowing are mentioned as e~amples o~
suitable emulsiiying agents: alkylsulphonates, higher chain alkyl sulphates, alkyltaurides and alkylsarcosides.
The iollowing ~ mpounds are mentioned as e3amples og polymerisation initiators: radical ~ormers such as azo compounds or inorganic and/or organic pero~ides such as potassium persulphate, cumene hydroperoxide and hydrogen pero~ide. The ~Eo~ides may also be used in combination with reducing agents such as triethanol-amine.
The terpolymers according to the present in~ention ~n readily be cross-linked pero.~idically or by high energy radiation. Suitable peroxides are those which decompo~e at temperatures in the range o~ irom 150 to 220C; ~or e~ample, tertiary butyl perbenzoate, dicumyl-pero~ide, 2 7 5-bis-(t-butylpero~y)-2,5-dimethylhe~ane a~d a,a-bis-(t-butylpero~)-diisopropyl~benzene.
Dependin~ u~ ~ ~ e acti~ity of the pero~idej the compou~ds ar~Yu~ed in quantities of ~rom 2 to 8 g, preferably ~rom 3 to 6 g per lO0 g of polymer.
The high.energy radiation em~loyed may be any ~orm o~ ionising radiation, e.g. r-rays, ~-ray~, a-rays, proton-neù-ton rays and ~ particles The radiation ~rom a 2-MEV-Van-der-Graaf electron.accelerator is pre-~erably Le A 19 019 ~l7279 employed.
Active ~illers must be added to the polymers i~ sui~able vulcanizates are to be obtained. Certain hal~-active ~illers may also be used, but the ~ield of application o~ the vulcanizates thus obtained is then very restricted because the mechanical properties obtained when using hald active fillers are not adequate. For a me-dium degree of hardness, for example, it is su~ficient to use from 50 to 60 parts of ~or example a FEF carbon - black. In order to obtain a good and optimum degree o~ cross-linking, so-oallëd cc-agents are prefer~ly added to the rubber mixtures~ These agents improve cross-linking when used in com~ination~th radical ~ormers such as peroxides or high energy radiation. Triallylcyanurate has proved to be a particularly suitable co-agent but bis- or tris-~unctional unsaturated compa~nds in the form o~
esbers or ethers of polyhy-dric alcohols sùch as those obtainable commercially ~or this purpose may also be n~ed. During the preparatio~ o~ the mi~ture~
sticki~g of the material to rollers or in inte~nal mi~ers i~ prevented~by the addition o~for ~le polyethylene wa~es, ~tearic acid or zi~c st~arate~
~ astly, age res~or~ in the form o~ sterically hindered phenols, polymerised 2,2,4-trimethyl-l,2- -dihydroquinoline, subs~tuted diphenylamines or phosphorus compounds such as tris-nonylphenyl-phosphite and polycarbodiimides may be used t~ Impn~
the resistance ~ hot air. A vulcanizate optimally adjusted to hot air ~geing should contain ca. O.l to 1.5 parts o~ the a~oresaid antioxidant3 and 4 parts o~ polycarbodiimide to lO0 parts of polymer.
The mechanical properties o~ the cross~ ked Le A 19 019 1 P727~7 terpolymers were measured as follows:
Mooney value of polymers: DIN 53 523 Ultimate tensile strength: DIN 53 504 (standard ring 1~
Elongation: DIN 53 504 (standard - ring 1) Compressio~set ASTM D 395, Method B
Hardness: DIN 53 505 Glass temperature: TMA
E~amples 1 to ~ describe the preparation o~
the terpolymers.
E~ample 1 The ~ollowing were introduced(under a nitrogen atmosphere) into a 40 1 autoclave:
22.0 kg distilled water, O.022 kg carbo~ymethylcellulo~e, 6.110 kg butyl acrylate, -4.450 kg vinyl acetate, 0,440 kg acrylonitrile, 0.022 kg azodiisobutyric acid nitrile.
The autclave was then heated to 45C (the st~rer was adjusted to 200 rev~/min) and polymerisation was carried out for 40 hours. The polymer was then iiltered, washed and dried. Yield: 82~, ~oone~
(ML-4/100C ) = 52, N2 content (Kjeldahl): 1.22 =
4.60~ ACN, Tgl/Tg2 = 20C/28C, gel content in toluene (ultraceutri~uge): 1~
(comparison) The ~ollowing were introduced (under a nitrogen atmosphere) i~to a 40 1 autclave:
22.0 kg distilled water, 0.022 kg carboxymethylcellulose, ! 772797 6.368 kg butyl acrylate, 4.211 kg vinyl acetate, O.022 kg azodiisobutyric acid nitrile.
Continued a~ in Example 1.
Yield: 80%~ Mooney (ML-4/100C) = 42; Tgl/Tg2 =
- 27C/22C; Gel content in toluene (ultracentrfuge)~
4~ 9oJh.
(comparison) The.~llowing are introduced into a 4-litre polymerisation vessel under a nitrogen atm~sphere-20.0 kg distilled water, 0.5 kg alkylsulphonate (paraffin chain C10-Cl5), O.6 kg butyl acrylate, 0,4 kg vinyl acetate, 0.1 kg lN NaOH, 0.051 kg K2S208, 0.04 kg Triethanolamine.
The temperature i~ adjusted to 10C. After 15 minutes, the ~ollowing are added ~ a uni~orm rate over
The following are examples of vinyl esters: vinyl esters having from 1 to 4 C-atoms in the acyl chain, such as vinyl acetate, propionate and butyrate, preferably vinyl acetate.
The following are examples of unsaturated nitriles:
Acrylonitrile, which may be substituted by a methyl group or a chlorine atom, such as methacrylonitrile.
The present invention also provides a process for the preparation of the terpolyme.rs, characterised in that from 40 to 75 parts by weig~t of an acrylic acid ester, from 20 to 55 parts by ~eight of a vInyl ester, and from 0.5 to 9 parts by weight of a unsaturated nitr~le are polymerised in aqueous suspension or emulsion in the presence of a monomersoluble and or water-soluble polymerisat~on initiator at temperatures of from 0 to 60C, preferably of from 10 to ~ ~ - 4 -.
50C5 to a conYersion o~ up to 90~, pre~erably o~
up to 80%.
The dispersing and emulsi~ying agents and the polymerisation initiators which may be used are generally known.
E~amples of suitable dispersing agen-ts include carboxymethylcellulose and methylcellulose.
~ he ~ollowing are mentioned as e~amples o~
suitable emulsiiying agents: alkylsulphonates, higher chain alkyl sulphates, alkyltaurides and alkylsarcosides.
The iollowing ~ mpounds are mentioned as e3amples og polymerisation initiators: radical ~ormers such as azo compounds or inorganic and/or organic pero~ides such as potassium persulphate, cumene hydroperoxide and hydrogen pero~ide. The ~Eo~ides may also be used in combination with reducing agents such as triethanol-amine.
The terpolymers according to the present in~ention ~n readily be cross-linked pero.~idically or by high energy radiation. Suitable peroxides are those which decompo~e at temperatures in the range o~ irom 150 to 220C; ~or e~ample, tertiary butyl perbenzoate, dicumyl-pero~ide, 2 7 5-bis-(t-butylpero~y)-2,5-dimethylhe~ane a~d a,a-bis-(t-butylpero~)-diisopropyl~benzene.
Dependin~ u~ ~ ~ e acti~ity of the pero~idej the compou~ds ar~Yu~ed in quantities of ~rom 2 to 8 g, preferably ~rom 3 to 6 g per lO0 g of polymer.
The high.energy radiation em~loyed may be any ~orm o~ ionising radiation, e.g. r-rays, ~-ray~, a-rays, proton-neù-ton rays and ~ particles The radiation ~rom a 2-MEV-Van-der-Graaf electron.accelerator is pre-~erably Le A 19 019 ~l7279 employed.
Active ~illers must be added to the polymers i~ sui~able vulcanizates are to be obtained. Certain hal~-active ~illers may also be used, but the ~ield of application o~ the vulcanizates thus obtained is then very restricted because the mechanical properties obtained when using hald active fillers are not adequate. For a me-dium degree of hardness, for example, it is su~ficient to use from 50 to 60 parts of ~or example a FEF carbon - black. In order to obtain a good and optimum degree o~ cross-linking, so-oallëd cc-agents are prefer~ly added to the rubber mixtures~ These agents improve cross-linking when used in com~ination~th radical ~ormers such as peroxides or high energy radiation. Triallylcyanurate has proved to be a particularly suitable co-agent but bis- or tris-~unctional unsaturated compa~nds in the form o~
esbers or ethers of polyhy-dric alcohols sùch as those obtainable commercially ~or this purpose may also be n~ed. During the preparatio~ o~ the mi~ture~
sticki~g of the material to rollers or in inte~nal mi~ers i~ prevented~by the addition o~for ~le polyethylene wa~es, ~tearic acid or zi~c st~arate~
~ astly, age res~or~ in the form o~ sterically hindered phenols, polymerised 2,2,4-trimethyl-l,2- -dihydroquinoline, subs~tuted diphenylamines or phosphorus compounds such as tris-nonylphenyl-phosphite and polycarbodiimides may be used t~ Impn~
the resistance ~ hot air. A vulcanizate optimally adjusted to hot air ~geing should contain ca. O.l to 1.5 parts o~ the a~oresaid antioxidant3 and 4 parts o~ polycarbodiimide to lO0 parts of polymer.
The mechanical properties o~ the cross~ ked Le A 19 019 1 P727~7 terpolymers were measured as follows:
Mooney value of polymers: DIN 53 523 Ultimate tensile strength: DIN 53 504 (standard ring 1~
Elongation: DIN 53 504 (standard - ring 1) Compressio~set ASTM D 395, Method B
Hardness: DIN 53 505 Glass temperature: TMA
E~amples 1 to ~ describe the preparation o~
the terpolymers.
E~ample 1 The ~ollowing were introduced(under a nitrogen atmosphere) into a 40 1 autoclave:
22.0 kg distilled water, O.022 kg carbo~ymethylcellulo~e, 6.110 kg butyl acrylate, -4.450 kg vinyl acetate, 0,440 kg acrylonitrile, 0.022 kg azodiisobutyric acid nitrile.
The autclave was then heated to 45C (the st~rer was adjusted to 200 rev~/min) and polymerisation was carried out for 40 hours. The polymer was then iiltered, washed and dried. Yield: 82~, ~oone~
(ML-4/100C ) = 52, N2 content (Kjeldahl): 1.22 =
4.60~ ACN, Tgl/Tg2 = 20C/28C, gel content in toluene (ultraceutri~uge): 1~
(comparison) The ~ollowing were introduced (under a nitrogen atmosphere) i~to a 40 1 autclave:
22.0 kg distilled water, 0.022 kg carboxymethylcellulose, ! 772797 6.368 kg butyl acrylate, 4.211 kg vinyl acetate, O.022 kg azodiisobutyric acid nitrile.
Continued a~ in Example 1.
Yield: 80%~ Mooney (ML-4/100C) = 42; Tgl/Tg2 =
- 27C/22C; Gel content in toluene (ultracentrfuge)~
4~ 9oJh.
(comparison) The.~llowing are introduced into a 4-litre polymerisation vessel under a nitrogen atm~sphere-20.0 kg distilled water, 0.5 kg alkylsulphonate (paraffin chain C10-Cl5), O.6 kg butyl acrylate, 0,4 kg vinyl acetate, 0.1 kg lN NaOH, 0.051 kg K2S208, 0.04 kg Triethanolamine.
The temperature i~ adjusted to 10C. After 15 minutes, the ~ollowing are added ~ a uni~orm rate over
3 hour~
5,4 kg butyi acrylate, and 3.6 kg vinyl acetate.
Stirri~g i~ continued for one hour after all the monomer has been added, ~he reaction is st~pped by hydroquinone, the reaction mi~ture is degassed and then precipitated with sodium chlorlde sol~tion.
Yield: 600~o Moone~ (ML-4/lOO"C) = 29; Tgl/Tg2 = -27C/30C;
Gel content in toluene (ultracentri~uge) : 1%.
E~am~le 4 The ~ollowing are introduced into a 40 1 pol~-merisation tank under a nitrogen atmosphere:
1 72~9 20000 kg distilled water, 0.50 kg alkylsulphonate ¦paraf~in chain C10-Cl5), 0.10 kg lN NaO~, O.60 kg butyl acrylate, 0.35 kg vi~yl acetate, 0.05 kg acrylonitrile, 0.04 kg ~2S208 (in 1.96 kg distilled water)~
0.08 kg Triethanolamine (in 0.92 kg distilled water).
~ he temperature is adjusted to 12C and a~ter 5 minu~es, the ~ollowing are added at a uni~orm rate over 3 hours:
5.40 kg butyl acrylate, 3.15 kg vinyl acetate, O.45 kg acrylonitrile.
As soon as all the monomer has been added, the reaction is stopped with sodium dithionite, the reaction mi~ture is degassed and th~ precipitated with sodium c~oride solution.
Yield: 70~o, Mooney (ML-4/100C) = 46,N2 content (Ejeldahl): 1.36 = 502~ acrylonitrile; Tgl/Tg2 =
-16C/28C.
Gel content in toluene (ultracentrifuge)~
The vulcanizates shown in the Table contain ~ part of stearic acid, 50 parts o~ FEF carbon black, 1 part o~ styrenised diphenylamine, 4 parts o~
polycarbodiimide, 3 parts o~ triallylcyanurate and
5,4 kg butyi acrylate, and 3.6 kg vinyl acetate.
Stirri~g i~ continued for one hour after all the monomer has been added, ~he reaction is st~pped by hydroquinone, the reaction mi~ture is degassed and then precipitated with sodium chlorlde sol~tion.
Yield: 600~o Moone~ (ML-4/lOO"C) = 29; Tgl/Tg2 = -27C/30C;
Gel content in toluene (ultracentri~uge) : 1%.
E~am~le 4 The ~ollowing are introduced into a 40 1 pol~-merisation tank under a nitrogen atmosphere:
1 72~9 20000 kg distilled water, 0.50 kg alkylsulphonate ¦paraf~in chain C10-Cl5), 0.10 kg lN NaO~, O.60 kg butyl acrylate, 0.35 kg vi~yl acetate, 0.05 kg acrylonitrile, 0.04 kg ~2S208 (in 1.96 kg distilled water)~
0.08 kg Triethanolamine (in 0.92 kg distilled water).
~ he temperature is adjusted to 12C and a~ter 5 minu~es, the ~ollowing are added at a uni~orm rate over 3 hours:
5.40 kg butyl acrylate, 3.15 kg vinyl acetate, O.45 kg acrylonitrile.
As soon as all the monomer has been added, the reaction is stopped with sodium dithionite, the reaction mi~ture is degassed and th~ precipitated with sodium c~oride solution.
Yield: 70~o, Mooney (ML-4/100C) = 46,N2 content (Ejeldahl): 1.36 = 502~ acrylonitrile; Tgl/Tg2 =
-16C/28C.
Gel content in toluene (ultracentrifuge)~
The vulcanizates shown in the Table contain ~ part of stearic acid, 50 parts o~ FEF carbon black, 1 part o~ styrenised diphenylamine, 4 parts o~
polycarbodiimide, 3 parts o~ triallylcyanurate and
4.5 parts o~ 1,3-bis-(t-butylpero~y)-diisop~opylbenzene to 100 parts o~ polymer.
The mechanical properties were measured on 4 ~m --thick DIN ~laps which had been vulcanized at 170C
~or 20 minutes. The samples ~or testing were not tempered~
~ .11 7279~
Pr~erties of vulcanizate Suspension polymer accord-ing to Example 1 2 Emul~ion polymer accord-ing to ~xample 3 4 Tensile strength DIN 53 504 ~MPa] 9.48~8 9OO 9.2 Elongation at break DIN 53 504 230 100 190 220 [hl Shore hard~ess [Shore A~ at 20C65 83 58 65 at 70 C 52 59 52 56 Compressio~s~et~
according to ASTM D 395, method B
70 h 150C [%] 32,2 26.7 ~7.3 33-7 Ageing in hot air (10 da~s at 170C):
Tensile strength [MPa~ 10.6 9.6 7.5 10.0 Elongation at break Colo j 140 60 140 160 Shore hard~ess [Shore Aj 83 87 72 81 Ageing in oil (7 days ASTM oil II
up to 150C):
Tensile strength [MPa3 9.2 7.3 6.5 7.8 Elongation at break [/0] 240 105 190 235 Shore hardness [Shore A¦ 56 73 43 56
The mechanical properties were measured on 4 ~m --thick DIN ~laps which had been vulcanized at 170C
~or 20 minutes. The samples ~or testing were not tempered~
~ .11 7279~
Pr~erties of vulcanizate Suspension polymer accord-ing to Example 1 2 Emul~ion polymer accord-ing to ~xample 3 4 Tensile strength DIN 53 504 ~MPa] 9.48~8 9OO 9.2 Elongation at break DIN 53 504 230 100 190 220 [hl Shore hard~ess [Shore A~ at 20C65 83 58 65 at 70 C 52 59 52 56 Compressio~s~et~
according to ASTM D 395, method B
70 h 150C [%] 32,2 26.7 ~7.3 33-7 Ageing in hot air (10 da~s at 170C):
Tensile strength [MPa~ 10.6 9.6 7.5 10.0 Elongation at break Colo j 140 60 140 160 Shore hard~ess [Shore Aj 83 87 72 81 Ageing in oil (7 days ASTM oil II
up to 150C):
Tensile strength [MPa3 9.2 7.3 6.5 7.8 Elongation at break [/0] 240 105 190 235 Shore hardness [Shore A¦ 56 73 43 56
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Terpolymer consisting of 60 to 80% by weight of an acrylic acid ester, 12 to 34% by weight of a vinyl ester and 0.5 to 12% by weight of an unsaturated nitrile, said terpolymer having a Mooney viscosity of at least 40 (ML - 4'/100°C), as well as a hardness difference (Shore A) between 20 and 70°C of less than 14 points, the vulcanisation product thereof having, without being after-heated, a tensile strength of greater than 9.0 MPa, at an elongation of over 180%, and a residual compression (70 H/150°C) of less than 35%.
2. Terpolymer according to claim 1, containing 3 to 6% by weight of an unsaturated nitrile.
3. Terpolymer according to claim 1 or 2, which consists of two phases, and the glass transition point of one phase is below 268 K.
4. Process for the preparation of the polymers according to claim 1, characterised in that 40 to 75 parts by weight of an acrylic acid ester, 20 to 55 parts by weight of a vinyl ester and 0.5 to 9 parts by weight of an unsaturated nitrile are polymerised in aqueous suspension or emulsion in the presence of a monomer-soluble or water-soluble polymerisation initiator at a temperature of from 0 to 60°C, up to a conversion of not greater than about 90%.
5. Process according to claim 4, characterised in that the polymerisation is carried out at a temperature of from 10 to 50°C.
6. Process according to claim 4, characterised in that the polymerisation is carried out up to a conversion of not greater than about 80%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2843041.3 | 1978-10-03 | ||
| DE19782843041 DE2843041A1 (en) | 1978-10-03 | 1978-10-03 | TERPOLYMERS OF ACRYLIC ACID ESTERS, VINYL ESTERS AND UNSATURATED NITRILES AND THEIR PRODUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1172797A true CA1172797A (en) | 1984-08-14 |
Family
ID=6051241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336720A Expired CA1172797A (en) | 1978-10-03 | 1979-10-01 | Terpolymers of acrylic acid esters, vinyl esters and unsaturated nitriles and their preparation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0009731B1 (en) |
| JP (1) | JPS5923565B2 (en) |
| CA (1) | CA1172797A (en) |
| DE (2) | DE2843041A1 (en) |
| ES (1) | ES484646A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215962A (en) * | 2022-09-15 | 2022-10-21 | 拓迪化学(上海)有限公司 | Preparation method of binder resin for protecting edge of positive pole piece of lithium battery, binder resin and insulating glue |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57121046A (en) * | 1981-01-21 | 1982-07-28 | Denki Kagaku Kogyo Kk | Composition for vulcanizing elastomer |
| DE3302124A1 (en) * | 1983-01-22 | 1984-07-26 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS |
| US5387329A (en) * | 1993-04-09 | 1995-02-07 | Ciba Corning Diagnostics Corp. | Extended use planar sensors |
| US7756301B2 (en) | 2005-01-26 | 2010-07-13 | Honeywell International Inc. | Iris recognition system and method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2548186A (en) * | 1950-02-25 | 1951-04-10 | Goodrich Co B F | Interpolymers of an alkyl acrylate, an aromatic monoolefin, and a vinyl ester of an aromatic monocarboxylic acid |
| DE1151661B (en) * | 1961-08-30 | 1963-07-18 | Basf Ag | Process for the production of frost- and electrolyte-resistant polymer dispersions |
| US3729772A (en) * | 1972-03-13 | 1973-05-01 | Atwood Vacuum Machine Co | Torsion bar hold-open hinge |
-
1978
- 1978-10-03 DE DE19782843041 patent/DE2843041A1/en not_active Withdrawn
-
1979
- 1979-09-21 DE DE7979103570T patent/DE2962059D1/en not_active Expired
- 1979-09-21 EP EP79103570A patent/EP0009731B1/en not_active Expired
- 1979-10-01 CA CA000336720A patent/CA1172797A/en not_active Expired
- 1979-10-02 JP JP54126478A patent/JPS5923565B2/en not_active Expired
- 1979-10-02 ES ES484646A patent/ES484646A1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215962A (en) * | 2022-09-15 | 2022-10-21 | 拓迪化学(上海)有限公司 | Preparation method of binder resin for protecting edge of positive pole piece of lithium battery, binder resin and insulating glue |
| CN115215962B (en) * | 2022-09-15 | 2022-12-06 | 拓迪化学(上海)有限公司 | Preparation method of binder resin for edge protection of lithium battery positive pole piece, binder resin and insulating glue |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2843041A1 (en) | 1980-04-24 |
| JPS5550005A (en) | 1980-04-11 |
| JPS5923565B2 (en) | 1984-06-02 |
| EP0009731B1 (en) | 1982-02-03 |
| ES484646A1 (en) | 1980-06-16 |
| EP0009731A1 (en) | 1980-04-16 |
| DE2962059D1 (en) | 1982-03-11 |
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| MKEX | Expiry |