CA2052487A1 - Polyurethane and method of preparing the same - Google Patents
Polyurethane and method of preparing the sameInfo
- Publication number
- CA2052487A1 CA2052487A1 CA 2052487 CA2052487A CA2052487A1 CA 2052487 A1 CA2052487 A1 CA 2052487A1 CA 2052487 CA2052487 CA 2052487 CA 2052487 A CA2052487 A CA 2052487A CA 2052487 A1 CA2052487 A1 CA 2052487A1
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- modified lignin
- set forth
- weight
- polyol compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 10
- 229920005610 lignin Polymers 0.000 claims abstract description 56
- 229920005862 polyol Polymers 0.000 claims abstract description 31
- -1 polyol compound Chemical class 0.000 claims abstract description 27
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 239000011276 wood tar Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 244000166124 Eucalyptus globulus Species 0.000 claims description 4
- 241001223353 Pinus caribaea Species 0.000 claims description 3
- 235000009324 Pinus caribaea Nutrition 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 229940125898 compound 5 Drugs 0.000 claims 1
- 239000006260 foam Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920005611 kraft lignin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- KGZJRXKGJRJKCB-UHFFFAOYSA-N hanf Chemical compound C=1C=CC=CC=1CC(C(=O)NC(CCCNC(N)=N)C(=O)NC(CC=1C=CC(O)=CC=1)C(O)=O)NC(=O)C(CO)NC(=O)C(CC(N)=O)NC(=O)C(CS)NC(=O)CNC(=O)C(CC(C)C)NC(=O)CNC(=O)C(CO)NC(=O)C(CCC(N)=O)NC(=O)C(C)NC(=O)CNC(=O)C(C(C)CC)NC(=O)C(CCCNC(N)=N)NC(=O)C(CC(O)=O)NC(=O)C(CCSC)NC(=O)C(CCCNC(N)=N)NC(=O)CNC(=O)CNC(=O)C(NC(=O)C(CS)NC(=O)C(CO)NC(=O)C(CO)NC(=O)C(CCCNC(N)=N)NC(=O)C(CCCNC(N)=N)NC(=O)C(CC(C)C)NC(=O)C(N)CO)CC1=CC=CC=C1 KGZJRXKGJRJKCB-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Polyurethane comprising a modified lignin as a hard segment, and polyurethane comprising a modified lignin as a hard segment and a polyol compound as a soft segment, and a method of preparing the same. The polyurethane has good mechanical and thermal properties.
Polyurethane comprising a modified lignin as a hard segment, and polyurethane comprising a modified lignin as a hard segment and a polyol compound as a soft segment, and a method of preparing the same. The polyurethane has good mechanical and thermal properties.
Description
'91-1~9-~'~ 15:1 1 T~l~'EDH Ll~ PFIrENr OFFICE P.'l ~5~
~OVE~ POLYURETHANE AND MErrHOD OF PR~PA~ING THE S~ME
~AC~GROUND O~ TEIE I~VENTION
1. ~ield of the lnvention S This invention relates to a novel polyure-thane, in particular a novel polyurethane comprising a modified lignin as a haLd segment tharein, ~nd a meth~d of preparing the same.
~OVE~ POLYURETHANE AND MErrHOD OF PR~PA~ING THE S~ME
~AC~GROUND O~ TEIE I~VENTION
1. ~ield of the lnvention S This invention relates to a novel polyure-thane, in particular a novel polyurethane comprising a modified lignin as a haLd segment tharein, ~nd a meth~d of preparing the same.
2. Disclosure of the Prior Art In the past, there were known polyurethanes of many kinds. I~ general, these polyurethanes could be prepared by stoichiometrically reacting polyol or polyester with diisocya~te in accordance with a so-called prepolymer method or direct preparation method.
Recently, Japanese Patent Public Disclosure No.
~89823/1989 describes that an improved polyurethane is obtained by using a cellulosic substance, hemicellulosic substance and lignin substance, which are contained in a natural by-product or ayricultural was~e product, as a hara segment in the polyurethane, whereby mechanical and thermal properties of the polyurethana can be improved and a low-cost polyurethane can be prepared.
However, since kraft lignin has a large molecular weight, the viscosity of kraft lignin di~solved i~
polyeth~lene glycol is high, and furthermore it is less compatible with dipheny}methane diisocyanate. Thus, uniform polyurethane cannot be obtained.
Now, a wood tar distillation residue from a '91--i~l9--~" lC '~l rH~'E L11~1 L~ H I E~ FF LCE F' . 5 2~
hroad- leaved tree and needle-leav~d tree. s~lch as eucalyptus, Caribbean pine or the like c~n bc pxoduced abundantly as an industrial b~product in a ~anufacturing industry for car~on m~terials or the like, but -the way to utilize it is yet less. In paxticular it is a~sired to effectively utilize a modified lignin which is rnuch contained in the residue SUMMARY OF TI~E INVENTION
It is an o~ject of -~his invention to provide polyurethane in which a modified lignin is effectively used as a raw material there~o~e, and to pro~ide a method of preparing the same.
The above ob~ ect is accomplished by proviaing polyurethane which comprises a modified lignin as a hard segment, or comprises a moaified li~nin as a hard segment and a polyol compound as a soft segment.
The above ohject is also accomplished by providing a method of preparlng polyurethane which comprises reacting a modified lignin, diisocyanate and a polyol compound to form the poly~rethane comprising the modified lignin as a hard se~ment.-~he thus-obtained polyuxethane comprising the modified lignin as the hard segment has good mechanical and thermal propert~es as compared with the prior polyurethane In aadition, the inventive polyurethane is more economical than the prior polyurethane and improves environment.
~ lJY-_CJ lC,:S~ rH~ELJH ~H~ IE~`ll OFF~C~ P,~
~5~
DETAILED DESCRIPT:LON OF PRE~ERRE~ EMBODIMENTS
Polyurethane according to this invention inoludes a hard segment region at least a part of which is formed by a modi~ied lignin and a so~t ~egment region which i~
constructed by a long chain diol residue component. In addition, the polyurethane according to this invention includes a polyol compound in the soft segment reg.ion.
The modified lignin which is ~sed in this invention ~an be obtained ~rom a wood tar distillation residue which is forme~ due to dry distillation of the broad-leaved tree or needle-leaved tree. The thu~-obt~ined modified lignin (the wood tar distillation residue) may be a modified li~no-cellulose.
The modifed lignin in this invention may have a molecular weight of about 300 to about 2,000, a hydroxyl group content of about 3 to about 20 mmol/g and a carboxyl group content-of about 0.2 about 2.0 mmol~g.
In this invention, there is used a solvent-soluhle modifed lig~in.
The modified lignin in this in~ention has, for example, a number average molecul~r weight of 540 and a weight average molecular weight of 1,300 In contrast to this invention, lignin in the prior art, for example, kraft lignin has, for example, a num~er average molecular weight o 1,200 and a weight average molecular weight of 2,200. Since the molecular weight of the modi~ie~ lignin is very lower than that of the pxior lignin, viscosity of a solution of the modified lignin in polyethylene glycol -- 3 -- .
19-~'5 15:5~ T~liED~ Lf`~ RrE~`II U~FIC~ P.7 is lower than that of the prior L;gnin. In addition, the modified lignin is compatible w~th diphenylmethane diisoc~anate and can be unrestric-tedly dissolved.
Therefore, by using an appropria-te amount of the modified liynin, it is possible to prepare the uni~orm polyurethane as compared with the polyurethane obtained from tha prior li~nin.
In this invention, it is pre~erred to prep~re the polyurethane according to ~he so-called prepolymer method. Prepolymer of polyurethane according to this inve~tion can be prepared by ~irst aissolving the modi~ied liynin in ~he polyol compoun~, adding the diisocyanate component -to the ~olution with stirring and allowing these components to polymerize. A ~ilm ~nd resin can be o~tained b~ curing the thus-obtained prepolymex with a catalyst or hea~ing. In addition, a foam can be obtained by adding water (or a blowing agent), a foam stabilizer and a catalyst to the above prepolymer and allowing it to react.
Polyisocyanate used in this i~vention is the same as that used in preparing the prior polyurethane. ~he polyuretha~e can include, for example, an aromatic isocyanate such as diphenvlmethane diisocyanate, toluylene diisocyanate or the like; an aliphatic isocyanate such as hexamethylene diisocyanate or the like; and a heterocyclic isocyana~e.
~urthermore, the polyol compound used in this invention i5 the sa~e as that used in preparing the prior ELlri L~ IE~`Jl UF-t'~
2i~.5~
polyure~hanF~ Th~ polyol compound can include, for e~ample, polyether se~ies such as poly~thylene glycol, polypropylene glycol or the like and a synthetic polyol c~mpouna of polyester series su~h as adipate, polycaprolactone or the l:ike.
For the polymerization catalyst, convenkional amine and tin series catalyst can be used.
For the foam stablizer, conventional ~ilicone series such as silicone, a block copolymer o~ dimethyl polysiloxame and polyether or the like can b~ used.
The proportion of the polyol compound to -the mo~ified lignin to be uséd is ~ to 5,000 pa~ts by ~eight, p~eferably 0 to 3,000 parts by weigh-t of ~he polyol compound, based on 100 parts by weight o~ the modified lignin.
Also, the proportion o~ the diisocyanate -to be used is 10 to 1,000 pa~ts b~ weight, preferably 10 to 900 parts by welght, based on 100 parts b~ weight of the sum o~ said modifiea li~nin and said polyol compound. In case of ma~ing the foam, the water and ~oam stabilizer ~re used in an a~ount of 0.1 to 20 parts by weight, preferably 0.5 to 10 part~ by weight and 0~001 to 0.5 parts by weight, pre~erably 0.02 to 0.25 parts by weight, respectively, based on 1 no paxts b~ weight of the sum o~
said modified ligni~, said polyol compound and Saia diisoc~anate.
The preparation o~ polyurethane according to this invention can be carried out by dissolving the modified '91-EIY-~C 15:53 T~KEDI~I LHW ~ PRiENT OFFICE p,9 lignin i.n the polyol ~ompound which is used both ~or solvent and for re~ctant, a~ding di.isocyan~te to the obtained solution and allowing these components to react.
For the other solvent, for example, tetr~hydro-uran~
S aioxane or the like can be us~d. In -this case, it is possible to dissolving the modified lignin and polyol compound in the solven-t, ~dding diisocyana-te to the obtained solution and allowing them to react. ~he pxoportion of said polyol compouna to be used in ~his reactlon is 0 to 95 parts by weight, pre~erably 0 to 90 parts by weight, based on 100 parts by weight o the moaified lignin.
According to this invention, in case of using the polyol compound as a solvent, it is possible to obtain the polyurethane comprising 5 -to 25 ~ by weight, preferably 10 to 25 ~ by weight oE the modi~ied lignin; 5 to 90 ~ by weight, pre~exably 10 to 70 % by weight, o the polyol compound; and 5 to 90 ~ by wei~ht, pre~erably, 10 to 70 ~ by weight, o~ s~id diisocyanate. In case of using the solvent ~ther than the polyol compound, it is possible to obtain the polyurethane comprising 5 to 25 by wiehgt, preferably 10 to 25 % by weight, of the modified lign~n; 0 to 90 % by weight, preferably 5 to 70 by weight, of the polyol compound; ~nd 0 to 90 % ~y weight, preferably 5 to 70 ~ by weight, of diisocyanate.
In general, the weight ratio of polyol/~odified lignin in the reaction produ~t is preferably in a range o~ 0 to 20, preferably 0 to 10.
'91-E~9-2C 15:53 TI~ EDR LQW .~ P~llE~`II OFFICE P. iE~
Since the polyurethane o-E this invention includes the modified lignin as the hard segment ~or polyurethane, it possesses good mechanical and-thermal properties.
Furthermore, the modified lignin is uniformly contained s as the ha~d se~ment ln the polyurethane in an appropriate proportion, whereby it b~comes possible ko appropriately adjust the mechanical and thermal proper-ties.
In addition, the modifed li~nin is very ch~ap, s~nce a use application thereo~ has not been de~eloped ana thus it has been treatea as an industrial was~e.
A1so, in the polyure~hane of this invention, it is possible to easily control properties o~ polyur~thane by changing the proportion of the soft segment compr.~sing the polyol compound and the hard segmen~ comprising the modified lignin.
~ext, this invention will be in detail aescribed with reference to ~n embodiment thereof but is not subject to restriction o~ the basis of the ~oltowing description~
Example 1 A modified lignin was obtained by pyrolizing a eucalyptus, distilling the thus-obtained tar content and recovering a residue. ~he modi~iea lig~in has a hydroxyl group content o~ 5.8 mmol/g, a carboxyl group content o~
0.8 mmol/g, a nu~ber average molecular welght (Mn) of 540, a weight average molecular ~Mw) of 1,200 and a molecular-weight aistributio~ ~M~Mn) o~ 2 2. ~he modified lignin was dlssolve.d in polypropylene glycol iY~ r~ EL~ L~:~W ~ ilE~ )F`F L~E ~. 11 (Functionallty of 3, Molecular Weight ok 400). To 100 parts by welght of the polypropylene ~lycol solution, diphenylme~hane diisocyanate was ~dded ln a predetermlned amount so as to attain NCO/OH of 1.2, with stirring. Two parts by weight of water were added as a blowing a~ent and two parts by weight of silicone were added as a foarn stabili2er For a catalyst, dibutyltin laurate was used For the ~h~s-obtaine~ polyurethane foam, compressive strength and modulus of ela~ticity were measured. The re~ults are shown in Table 1.
Table 1 Compressive Strength and Modulus of Elastici-ty of Foam . . _ Compressive Mod~lu~ of Lignin ContentStrength Elasticity lS (~) (105Pa) (MPa~
~ 3.8~ 9~78 4.17 11.24 4~44 15.27 2~ 4.96 10.0 ~0 As mentioned above, the polyuxethane according to this invention has good mechanical strength and heat resistance as compared with the prior polyurethane since it uniformly contains the modified lignin as the hard segment for polyurethane. In addition, it is possible to adjust the mechanical strength and heat resistanca.
Furthermore, since the raw ~aterial in ~his invention is th2 industrial waste in the carbon chemi~al '91-~9-~5 15 5~1 T~ ELJ~l LrlW ~ Pl ITENT OFFICE P. 12 ~52~
industry, its cost is very cheap Accordin~ly, this invention resides in that the material which had no use i~ the past and was uselessly renounced ls utilized as a raw material for manufac-t~ring polyuret~ane which is at present usea in many ~iel~.
This invention attains the improvement of environment and thus is useful.
Recently, Japanese Patent Public Disclosure No.
~89823/1989 describes that an improved polyurethane is obtained by using a cellulosic substance, hemicellulosic substance and lignin substance, which are contained in a natural by-product or ayricultural was~e product, as a hara segment in the polyurethane, whereby mechanical and thermal properties of the polyurethana can be improved and a low-cost polyurethane can be prepared.
However, since kraft lignin has a large molecular weight, the viscosity of kraft lignin di~solved i~
polyeth~lene glycol is high, and furthermore it is less compatible with dipheny}methane diisocyanate. Thus, uniform polyurethane cannot be obtained.
Now, a wood tar distillation residue from a '91--i~l9--~" lC '~l rH~'E L11~1 L~ H I E~ FF LCE F' . 5 2~
hroad- leaved tree and needle-leav~d tree. s~lch as eucalyptus, Caribbean pine or the like c~n bc pxoduced abundantly as an industrial b~product in a ~anufacturing industry for car~on m~terials or the like, but -the way to utilize it is yet less. In paxticular it is a~sired to effectively utilize a modified lignin which is rnuch contained in the residue SUMMARY OF TI~E INVENTION
It is an o~ject of -~his invention to provide polyurethane in which a modified lignin is effectively used as a raw material there~o~e, and to pro~ide a method of preparing the same.
The above ob~ ect is accomplished by proviaing polyurethane which comprises a modified lignin as a hard segment, or comprises a moaified li~nin as a hard segment and a polyol compound as a soft segment.
The above ohject is also accomplished by providing a method of preparlng polyurethane which comprises reacting a modified lignin, diisocyanate and a polyol compound to form the poly~rethane comprising the modified lignin as a hard se~ment.-~he thus-obtained polyuxethane comprising the modified lignin as the hard segment has good mechanical and thermal propert~es as compared with the prior polyurethane In aadition, the inventive polyurethane is more economical than the prior polyurethane and improves environment.
~ lJY-_CJ lC,:S~ rH~ELJH ~H~ IE~`ll OFF~C~ P,~
~5~
DETAILED DESCRIPT:LON OF PRE~ERRE~ EMBODIMENTS
Polyurethane according to this invention inoludes a hard segment region at least a part of which is formed by a modi~ied lignin and a so~t ~egment region which i~
constructed by a long chain diol residue component. In addition, the polyurethane according to this invention includes a polyol compound in the soft segment reg.ion.
The modified lignin which is ~sed in this invention ~an be obtained ~rom a wood tar distillation residue which is forme~ due to dry distillation of the broad-leaved tree or needle-leaved tree. The thu~-obt~ined modified lignin (the wood tar distillation residue) may be a modified li~no-cellulose.
The modifed lignin in this invention may have a molecular weight of about 300 to about 2,000, a hydroxyl group content of about 3 to about 20 mmol/g and a carboxyl group content-of about 0.2 about 2.0 mmol~g.
In this invention, there is used a solvent-soluhle modifed lig~in.
The modified lignin in this in~ention has, for example, a number average molecul~r weight of 540 and a weight average molecular weight of 1,300 In contrast to this invention, lignin in the prior art, for example, kraft lignin has, for example, a num~er average molecular weight o 1,200 and a weight average molecular weight of 2,200. Since the molecular weight of the modi~ie~ lignin is very lower than that of the pxior lignin, viscosity of a solution of the modified lignin in polyethylene glycol -- 3 -- .
19-~'5 15:5~ T~liED~ Lf`~ RrE~`II U~FIC~ P.7 is lower than that of the prior L;gnin. In addition, the modified lignin is compatible w~th diphenylmethane diisoc~anate and can be unrestric-tedly dissolved.
Therefore, by using an appropria-te amount of the modified liynin, it is possible to prepare the uni~orm polyurethane as compared with the polyurethane obtained from tha prior li~nin.
In this invention, it is pre~erred to prep~re the polyurethane according to ~he so-called prepolymer method. Prepolymer of polyurethane according to this inve~tion can be prepared by ~irst aissolving the modi~ied liynin in ~he polyol compoun~, adding the diisocyanate component -to the ~olution with stirring and allowing these components to polymerize. A ~ilm ~nd resin can be o~tained b~ curing the thus-obtained prepolymex with a catalyst or hea~ing. In addition, a foam can be obtained by adding water (or a blowing agent), a foam stabilizer and a catalyst to the above prepolymer and allowing it to react.
Polyisocyanate used in this i~vention is the same as that used in preparing the prior polyurethane. ~he polyuretha~e can include, for example, an aromatic isocyanate such as diphenvlmethane diisocyanate, toluylene diisocyanate or the like; an aliphatic isocyanate such as hexamethylene diisocyanate or the like; and a heterocyclic isocyana~e.
~urthermore, the polyol compound used in this invention i5 the sa~e as that used in preparing the prior ELlri L~ IE~`Jl UF-t'~
2i~.5~
polyure~hanF~ Th~ polyol compound can include, for e~ample, polyether se~ies such as poly~thylene glycol, polypropylene glycol or the like and a synthetic polyol c~mpouna of polyester series su~h as adipate, polycaprolactone or the l:ike.
For the polymerization catalyst, convenkional amine and tin series catalyst can be used.
For the foam stablizer, conventional ~ilicone series such as silicone, a block copolymer o~ dimethyl polysiloxame and polyether or the like can b~ used.
The proportion of the polyol compound to -the mo~ified lignin to be uséd is ~ to 5,000 pa~ts by ~eight, p~eferably 0 to 3,000 parts by weigh-t of ~he polyol compound, based on 100 parts by weight o~ the modified lignin.
Also, the proportion o~ the diisocyanate -to be used is 10 to 1,000 pa~ts b~ weight, preferably 10 to 900 parts by welght, based on 100 parts b~ weight of the sum o~ said modifiea li~nin and said polyol compound. In case of ma~ing the foam, the water and ~oam stabilizer ~re used in an a~ount of 0.1 to 20 parts by weight, preferably 0.5 to 10 part~ by weight and 0~001 to 0.5 parts by weight, pre~erably 0.02 to 0.25 parts by weight, respectively, based on 1 no paxts b~ weight of the sum o~
said modified ligni~, said polyol compound and Saia diisoc~anate.
The preparation o~ polyurethane according to this invention can be carried out by dissolving the modified '91-EIY-~C 15:53 T~KEDI~I LHW ~ PRiENT OFFICE p,9 lignin i.n the polyol ~ompound which is used both ~or solvent and for re~ctant, a~ding di.isocyan~te to the obtained solution and allowing these components to react.
For the other solvent, for example, tetr~hydro-uran~
S aioxane or the like can be us~d. In -this case, it is possible to dissolving the modified lignin and polyol compound in the solven-t, ~dding diisocyana-te to the obtained solution and allowing them to react. ~he pxoportion of said polyol compouna to be used in ~his reactlon is 0 to 95 parts by weight, pre~erably 0 to 90 parts by weight, based on 100 parts by weight o the moaified lignin.
According to this invention, in case of using the polyol compound as a solvent, it is possible to obtain the polyurethane comprising 5 -to 25 ~ by weight, preferably 10 to 25 ~ by weight oE the modi~ied lignin; 5 to 90 ~ by weight, pre~exably 10 to 70 % by weight, o the polyol compound; and 5 to 90 ~ by wei~ht, pre~erably, 10 to 70 ~ by weight, o~ s~id diisocyanate. In case of using the solvent ~ther than the polyol compound, it is possible to obtain the polyurethane comprising 5 to 25 by wiehgt, preferably 10 to 25 % by weight, of the modified lign~n; 0 to 90 % by weight, preferably 5 to 70 by weight, of the polyol compound; ~nd 0 to 90 % ~y weight, preferably 5 to 70 ~ by weight, of diisocyanate.
In general, the weight ratio of polyol/~odified lignin in the reaction produ~t is preferably in a range o~ 0 to 20, preferably 0 to 10.
'91-E~9-2C 15:53 TI~ EDR LQW .~ P~llE~`II OFFICE P. iE~
Since the polyurethane o-E this invention includes the modified lignin as the hard segment ~or polyurethane, it possesses good mechanical and-thermal properties.
Furthermore, the modified lignin is uniformly contained s as the ha~d se~ment ln the polyurethane in an appropriate proportion, whereby it b~comes possible ko appropriately adjust the mechanical and thermal proper-ties.
In addition, the modifed li~nin is very ch~ap, s~nce a use application thereo~ has not been de~eloped ana thus it has been treatea as an industrial was~e.
A1so, in the polyure~hane of this invention, it is possible to easily control properties o~ polyur~thane by changing the proportion of the soft segment compr.~sing the polyol compound and the hard segmen~ comprising the modified lignin.
~ext, this invention will be in detail aescribed with reference to ~n embodiment thereof but is not subject to restriction o~ the basis of the ~oltowing description~
Example 1 A modified lignin was obtained by pyrolizing a eucalyptus, distilling the thus-obtained tar content and recovering a residue. ~he modi~iea lig~in has a hydroxyl group content o~ 5.8 mmol/g, a carboxyl group content o~
0.8 mmol/g, a nu~ber average molecular welght (Mn) of 540, a weight average molecular ~Mw) of 1,200 and a molecular-weight aistributio~ ~M~Mn) o~ 2 2. ~he modified lignin was dlssolve.d in polypropylene glycol iY~ r~ EL~ L~:~W ~ ilE~ )F`F L~E ~. 11 (Functionallty of 3, Molecular Weight ok 400). To 100 parts by welght of the polypropylene ~lycol solution, diphenylme~hane diisocyanate was ~dded ln a predetermlned amount so as to attain NCO/OH of 1.2, with stirring. Two parts by weight of water were added as a blowing a~ent and two parts by weight of silicone were added as a foarn stabili2er For a catalyst, dibutyltin laurate was used For the ~h~s-obtaine~ polyurethane foam, compressive strength and modulus of ela~ticity were measured. The re~ults are shown in Table 1.
Table 1 Compressive Strength and Modulus of Elastici-ty of Foam . . _ Compressive Mod~lu~ of Lignin ContentStrength Elasticity lS (~) (105Pa) (MPa~
~ 3.8~ 9~78 4.17 11.24 4~44 15.27 2~ 4.96 10.0 ~0 As mentioned above, the polyuxethane according to this invention has good mechanical strength and heat resistance as compared with the prior polyurethane since it uniformly contains the modified lignin as the hard segment for polyurethane. In addition, it is possible to adjust the mechanical strength and heat resistanca.
Furthermore, since the raw ~aterial in ~his invention is th2 industrial waste in the carbon chemi~al '91-~9-~5 15 5~1 T~ ELJ~l LrlW ~ Pl ITENT OFFICE P. 12 ~52~
industry, its cost is very cheap Accordin~ly, this invention resides in that the material which had no use i~ the past and was uselessly renounced ls utilized as a raw material for manufac-t~ring polyuret~ane which is at present usea in many ~iel~.
This invention attains the improvement of environment and thus is useful.
Claims (18)
1. Polyurethane comprising a modified lignin as a hard segment.
2. Polyurethane as set forth in Claim 1, wherein said modified lignin is a wood tar distillation residue which is formed by dry distillation of a broad-leaved tree or needle-leaved tree.
3. Polyurethane as set forth in Claim 1, wherein said modified lignin is a wood tar distillation residue which is formed by dry distillation of eucalyptus or Caribbean pine.
4. Polyurethane as set forth in Claim 1, wherein said modified lignin is a modified ligno-cellulose.
5. Polyurethane as set forth in any of Claims 1 to 4, wherein said modified lignin has a molecular weight of 300 to 2,000 a hydroxyl group content of 3 to 20 mmol/g and a carboxyl group content of 0.2 to 2.0 mmol/g.
6. Polyurethane as set forth in any of Claims 1 to 4.
wherein said modified lignin has a number average molecular weight of 540, a weight average molecular weight of 1,200, a hydroxyl group content of 5.8 mmol/g and a carboxyl group content of 0.8 mmol/g.
wherein said modified lignin has a number average molecular weight of 540, a weight average molecular weight of 1,200, a hydroxyl group content of 5.8 mmol/g and a carboxyl group content of 0.8 mmol/g.
7. Polyurethane comprising a modified lignin as a hard segment and a polyol compound as a soft segment.
8. Polyurethane as set forth in Claim 7, wherein said modified lignin is a wood tar distillation residue which is formed by dry distillation of a broad-leave tree or needle-leaved tree.
9. Polyurethane as set forth in Claim 7, wherein said modified lignin is a wood tar distillation residue which is formed by dry distillation of eucalyptus or Caribbean pine.
10. Polyurethane as set forth in Claim 7, wherein said modifed lignin is a modified ligno-cellulose.
11. Polyurethane as set forth in any of Claim 7 to 10, wherein said modified lignin has a molecular with of 300 to 2,000, a hydroxyl group content of 3 to 20 mmol/g and a carboxyl group content of 0.2 to 2.0 mmol/g.
12. Polyurethane is set forth in any of Claims 7 to 10, wherein said modified lignin has a number average molecular weight of 540, a weight average molecular weight of 1,200, a hydroxyl group content of 5.8 mmol/g and a carboxyl group content of 0.8 mmol/g.
13. Polyurethane comprising a modified lignin, a polyol compound and diisocyanate having the following composition:
Modified Lignin 5 to 25 wt%
Polyol Compound 5 to 90 wt%
Diisocyanate 5 to 90 wt%
Modified Lignin 5 to 25 wt%
Polyol Compound 5 to 90 wt%
Diisocyanate 5 to 90 wt%
14. Polyurethane comprising a modified lignin, a polyol compound and diisocyanate having the following composition:
Modified Lignin 5 to 25 wt%
Polyol Compound 0 to 90 wt%
Diisocyanate 0 to 90 wt%
Modified Lignin 5 to 25 wt%
Polyol Compound 0 to 90 wt%
Diisocyanate 0 to 90 wt%
15. A method of preparing polyurethane which comprises reacting a modified lignin, diisocyanate and a polyol compound to form the polyurethane comprising the modified lignin as a hard segment.
16. A method of preparing polyurethane as set forth in Claim 15, wherein said modified lignin has a molecular weight of 300 to 2,000, a hydroxyl group content of 3 to 20 mmol/g and a carboxyl group content of 0.2 to 2.0 mmol/g.
17. A method of preparing polyurethane as set forth in Claim 15 or 16, which the proportion of said polyol compound to said modified lignin to be used is 0 to 5,000 parts by weight of the polyol compound based on 100 parts by weight of the modified lignin.
18. A method of preparing polyurethane as set forth in Claim 13, 14, or 15, wherein the proportion of said diisocyanate to be used is 10 to 1,000 parts by weight based on 100 parts by weight of the sum of said modified lignin and said polyol compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP274664/1990 | 1990-10-13 | ||
| JP02274664A JP3101701B2 (en) | 1990-10-13 | 1990-10-13 | New polyurethane and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2052487A1 true CA2052487A1 (en) | 1992-04-14 |
Family
ID=17544840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2052487 Abandoned CA2052487A1 (en) | 1990-10-13 | 1991-09-30 | Polyurethane and method of preparing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3101701B2 (en) |
| BR (1) | BR9104208A (en) |
| CA (1) | CA2052487A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9593221B1 (en) * | 2007-10-25 | 2017-03-14 | Maureen Kurple | Polyol, adhesive, resin, and tackifier—thixotropic additive |
| US9598529B2 (en) | 2013-08-13 | 2017-03-21 | Enerlab 2000 Inc. | Process for the preparation of lignin based polyurethane products |
| CN111454465A (en) * | 2020-04-15 | 2020-07-28 | 黎明化工研究设计院有限责任公司 | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4280888B2 (en) * | 2001-03-23 | 2009-06-17 | 独立行政法人産業技術総合研究所 | Process for producing biodegradable polycarboxylic acid ester / carboxylic acid |
| JP2010007001A (en) * | 2008-06-30 | 2010-01-14 | Hitachi Ltd | Unsaturated polyester resin composition |
-
1990
- 1990-10-13 JP JP02274664A patent/JP3101701B2/en not_active Expired - Lifetime
-
1991
- 1991-09-30 BR BR9104208A patent/BR9104208A/en unknown
- 1991-09-30 CA CA 2052487 patent/CA2052487A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9593221B1 (en) * | 2007-10-25 | 2017-03-14 | Maureen Kurple | Polyol, adhesive, resin, and tackifier—thixotropic additive |
| US10745513B1 (en) * | 2007-10-25 | 2020-08-18 | Organic Chemical | Polyol, adhesive, resin, and tackifier-thixotropic additive |
| US9598529B2 (en) | 2013-08-13 | 2017-03-21 | Enerlab 2000 Inc. | Process for the preparation of lignin based polyurethane products |
| CN111454465A (en) * | 2020-04-15 | 2020-07-28 | 黎明化工研究设计院有限责任公司 | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9104208A (en) | 1992-06-02 |
| JP3101701B2 (en) | 2000-10-23 |
| JPH04149229A (en) | 1992-05-22 |
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