CN1186364C - Polyurethane foam material and its preparation method - Google Patents
Polyurethane foam material and its preparation method Download PDFInfo
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- CN1186364C CN1186364C CNB021346313A CN02134631A CN1186364C CN 1186364 C CN1186364 C CN 1186364C CN B021346313 A CNB021346313 A CN B021346313A CN 02134631 A CN02134631 A CN 02134631A CN 1186364 C CN1186364 C CN 1186364C
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- aliphatic polycarbonate
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- polyurethane foam
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 22
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 55
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 47
- 239000004417 polycarbonate Substances 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000004814 polyurethane Substances 0.000 claims description 27
- 229920002635 polyurethane Polymers 0.000 claims description 27
- 235000011089 carbon dioxide Nutrition 0.000 claims description 21
- 125000005587 carbonate group Chemical group 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 17
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- -1 poly polypropylene carbonate Polymers 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000002924 oxiranes Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000006261 foam material Substances 0.000 claims description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract 3
- 150000004651 carbonic acid esters Chemical class 0.000 abstract 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000004872 foam stabilizing agent Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000005187 foaming Methods 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012611 container material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012999 compression bending Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960004692 perflenapent Drugs 0.000 description 1
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a novel polyurethane foam material and a preparation method thereof. The polyurethane foam material is an aliphatic polycarbonate type polyurethane foam material synthesized by using carbon dioxide as an initial raw material, wherein the content of carbonic acid ester base groups is between 15 wt% and 30 wt%. The preparation method of the polyurethane foam material comprises the following steps: aliphatic polycarbonate polyalcohol prepared from the carbon dioxide and epoxide by synthesis, the number average molecular weight of the aliphatic polycarbonate polyalcohol is smaller than 10000, the hydroxyl functionality is 2, 3 or greater than 3, and the mole fraction of a carbonic acid ester base group in a molecule is between 0.2 and 0.5; polyalcohol resin and diisocyanate and/or polycyanate react in the presence of catalysts, foaming agents, crosslinking agents or chain extenders, foam stabilizing agents and other auxiliary agents to obtain the polyurethane foam material of the present invention. The material has the characteristics of high strength, low combustion heat, and high abrasion resistance and hydrolysis resistance, and some varieties have high biodegradability; the material can be used as a furniture material, an automotive material, a thermal insulating material, a building material, a packing material, etc.
Description
Technical field
The present invention relates to a kind of novel with carbonic acid gas as aliphatic polycarbonate type polyurethane foam materials of the high carbon acid ester content of initial synthesis material and preparation method thereof.
Technical background
Preparing polyurethane material with carbonic acid gas as starting raw material is a new technology that grows up recent years, and resulting polyurethane material belongs to the aliphatic polycarbonate type polyurethane.Such polyurethane material has a lot of particular performances, compares as the polyether(poly)urethane material, and what its physical strength and wear resistance will be good is many; Compare with polyester type polyurethane material, it has better low temperature kindliness, hydrolytic resistance and oxidation-resistance.In addition, such polyurethane material of some kind also has favorable biological degradability.Past, aliphatic polycarbonate type polyurethane material mainly be with aliphatics or aromatic series small molecules carbonic ether as raw material, prepare how alcohol of aliphatic polycarbonate by ester-interchange method or cyclic carbonate ring-opening polymerization method etc., by crosslinked, chain extension etc. obtain again.Because the small molecules carbonic ether price that this process adopts is higher, the generation pollution is also bigger in the production process simultaneously, has seriously hindered the large-scale application of such material.The report of relevant such polyurethane material mainly concentrates on aspects such as elastomerics, coating, tackiness agent.
We with macromolecule loading double metal cyanide (ZL 89100701) as catalyzer, with carbonic acid gas and propylene oxide as raw material, obtain carbonate group mark (molar fraction) in the molecule at 0.2～0.5 the low sticking polyhydroxy fatty adoption carbonate resin (ZL 91109459) of liquid state by regulating polymerization, and with this resin as raw material, synthesize excellent property aliphatic polycarbonate type polyurethane elastomerics (Peng Han etc. chemistry world, 1995,8:426-428), carbonate group mass contg (% in this polyurethane elastomer, w) higher, generally between 15%～30%.
Kuyper etc. (US4826953) as catalyzer, adopt above-mentioned similar approach to obtain polyhydroxy fatty adoption carbonate resin with small molecules bimetal cyano complex, as raw material, prepare the Aliphatic Polycarbonate Polyurethanes foam with this resin.Yet, carbonate group mass contg in the resulting polyurethane foam of Kuyper (%, w) lower, about 3%～7%, approach polyether-type but not the polycarbonate polyurethane foam.
Summary of the invention
The purpose of this invention is to provide a kind of with the aliphatic acid ester carbonate type polyurethane foam materials of carbonic acid gas as the high carbon acid ester group content of initial synthesis material, it is compared with general polyurethane foam, have that intensity height, the combustion heat are low, wear resistance, characteristics that hydrolytic resistance is good, some kind has good biodegradability properties as polymerized thylene carbonate ethyl ester type polyurethane foam materials.Can be used as furniture material, automotive material, thermal insulation material, material of construction, wrapping material etc.
Another object of the present invention provides the preparation method of this polyurethane foamed material.
Polyurethane foamed material provided by the invention, be with carbonic acid gas as starting raw material synthetic aliphatic polycarbonate type polyurethane foam materials, wherein (% is w) between 15%～30% for the carbonate group mass contg.
This aliphatic polycarbonate type polyurethane foam materials is to adopt carbonic acid gas and epoxide to be no more than 10000 by molecular weight regulator synthetic number-average molecular weight, hydroxy functionality is 2,3 or higher, how pure the aliphatic polycarbonate of the molar fraction of carbonate group between 0.2～0.5 be in the molecule; Again by many alcohol of described aliphatic polycarbonate and vulcabond and/or the polymeric isocyanate of isocyanate index between 60-200, in the presence of catalyzer, whipping agent, crosslinked or chainextender, suds-stabilizing agent and other auxiliary agents, react synthetic.
How pure by carbonic acid gas and preparation of epoxides aliphatic polycarbonate among the present invention, used raw material epoxide, molecular weight regulator etc. can be the raw materials that prior art adopts.
Wherein with epoxide optimization ethylene oxide, propylene oxide and the butylene oxide ring of carbon dioxide reaction in one or several miscellany.
The mixture of one or several in the polyether polyol of the many alcohol of the aliphatics of the preferred hydroxy functionality of used molecular weight regulator 〉=2 or aromatic series, polyphenol, lower molecular weight (molecular weight is less than 1000), polyester polyol, the many alcohol of aliphatic polycarbonate etc.
The molar fraction of carbonic ether is preferably between the 0.20-0.45 between 0.2～0.5 in carbonic acid gas and the many alcohol of epoxide synthetic aliphatic polycarbonate.Its number-average molecular weight is less than 10000, preferably between the 500-5000.How pure described aliphatic polycarbonate preferred aliphat poly (propylene carbonate) be how pure, how pure the aliphatic poly ethylene carbonate is.
Described vulcabond is an organic compound, it contains at least two isocyanate groups, and be any or several mixture in known aliphatics or the aromatic isocyanate, common this class vulcabond and polymeric isocyanate have tolylene diisocyanate (TDI), 1,6-hexylidene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), diphenylmethanediisocyanate (MDI), carbodiimide modification MDI, poly isocyanate (PAPI).The consumption of isocyanic ester represents that with isocyanate index it is meant that the ratio of the amount of the needed isocyanic ester of all reactive hydrogen complete reactions in actual isocyanic ester consumption and the mixed system multiply by 100.Isocyanate index of the present invention is between 60-200, and between the preferred 90-105 of TDI based polyurethanes porous plastics isocyanate index, for MDI based polyurethanes porous plastics, isocyanate index is preferably between 90-130.
In the many alcohol of aliphatic polycarbonate and vulcabond and/or polymeric isocyanate prepared in reaction polyurethane foamed material, all can use conventional catalyzer, whipping agent, crosslinked or chainextender, suds-stabilizing agent and other auxiliary agents etc.
Wherein catalyzer has organo-metallic catalyst, mainly is tin class catalyzer such as di-n-butyltin dilaurate, stannous octoate; Tertiary amine catalyst such as triethylenediamine, N, N`-dimethylcyclohexylamine, two-(2-dimethylaminoethyl) ether, N`-methyl-N` (2-dimethylamino) ethyl piperazidine, N, N, N`, N`-tetramethyl--1,6-butanediamine, N, N-dimethylaminoethanol, N, N, N`, N`, N`-five methyl diethylentriamine, N, N`, N`, the N`-tetramethylethylened, one or several in the trolamine etc. perhaps use the composite use of tin class catalyzer and amines catalyst, catalyst consumption by weight, general alcohol resin more than 0.001-0.5 part/100 part.
The linking agent that is adopted or (with) chainextender is generally small-molecule substance, its molecule contain can with the reactive hydrogen of isocyanate reaction, and its molecular weight is below 500 usually, linking agent or (and) in the chainextender molecule reactive hydrogen number between 2-12, preferred 3-6, the linking agent that can adopt or (with) chainextender has the many alcohol of small molecules as glycerol, TriMethylolPropane(TMP), tetramethylolmethane, small molecules polyamine such as quadrol, diethylenetriamine, triethylene tetramine, water, molecular weight are lower than 500 polyethers or polyester polyol.Linking agent or (with) consumption of chainextender by weight, be generally less than 30 parts/alcohol resin more than 100 parts.By adjust linking agent or (with) consumption of chainextender, can adjust the stable and hardness of foamy.
Suds-stabilizing agent can be with containing sulfonic tensio-active agent, water miscible polyether silicone etc., its consumption by weight, general alcohol resin more than 0.1-6 part/100 part, preferred 0.7-2.5 part/alcohol resin more than 100 parts.
Whipping agent can adopt one or more in pneumatogen such as CFCs series, HCFCs series, HFCs series, pentane, perflenapent, PF 5070, hydrogen fluorohydrocarbon ether, liquid carbon dioxide or the like, the usage quantity of pneumatogen is alcohol resin more than 0-50 part/100 part generally, chemical foaming agent such as water, its consumption is alcohol resin more than 2-7 part/100 part generally, and perhaps pneumatogen and chemical foaming agent are mixed uses.
Also can add a certain amount of other auxiliary agents, as fire retardant, toughener, filler, oxidation inhibitor, photostabilizer etc. according to its concrete application requiring.
Main points of the present invention are to adopt carbonic acid gas and epoxide as raw material, the composite number average molecular weight is below 10000, hydroxy functionality is 2,3 or higher, how pure the aliphatic polycarbonate of carbonate group molar fraction between 0.2～0.5 be in the molecule, and how pure as raw material synthetic fat adoption carbonic ether type polyurethane foam with this.
The many alcohol of the aliphatic polycarbonate that the present invention relates to are method synthetic of announcing by ZL 91109459.8, the consumption of control molecular weight regulator, and the number-average molecular weight of the many alcohol of synthetic aliphatic polycarbonate is less than 10000, preferably between the 500-5000.Used epoxide can be one or several the miscellany in oxyethane, propylene oxide, the butylene oxide ring etc. when synthetic.Molecular weight regulator used when synthetic can how pure for the polyphenol or the aromatic series of alcohol more than the aliphatics of hydroxy functionality 〉=2, hydroxy functionality 〉=2, the polyether polyol of the lower molecular weight of hydroxy functionality 〉=2 (molecular weight is less than 1000), the polyester polyol of hydroxy functionality 〉=2 also can adopt one or several the mixture in the many alcohol of aliphatic polycarbonate etc. of hydroxy functionality 〉=2.Adopt this many alcoholic extract hydroxyl groups of method synthetic aliphatic polycarbonate functionality 〉=2, its molecular structure is as follows:
Wherein: R is aliphatics or aromatics group.M, n are the positive integer more than or equal to 1.F is the hydroxy functionality of many alcohol, f 〉=2.
Urethane foam involved in the present invention is with vulcabond and or polymeric isocyanate and contain the employing carbonic acid gas of two or more reactive hydrogens many alcohol reactions make as initial synthesis material synthetic aliphatic polycarbonate in the presence of catalyzer, whipping agent, crosslinked or chainextender, suds-stabilizing agent and other auxiliary agents.
The molecular backbone chains of the many alcohol of aliphatic polycarbonate of the present invention contain aliphatics alkylidene group and carbonate group repeating unit, and its character as has lower Tg between the how pure and mild polyether polyol of aliphatic polyester, preferably the room temperature kindliness; The aliphatic polycarbonate of some kind is alcohol how, as how pure and mild polymerized thylene carbonate second third ester polyol of polymerized thylene carbonate ethyl ester etc., has favorable biological degradability.
Adopt the how pure synthetic polyurethane material of aliphatic polycarbonate generally to have the character that some PAUR and polyether(poly)urethane are not had.As good solvent resistance, hydrolytic resistance, scale resistance etc.Provided by the invention is that raw material synthetic aliphatic polycarbonate type polyurethane foam materials has kept outside the above good performance with the carbonic acid gas, and more outstanding is has a very low combustion heat, manufactures fire-retardant product easilier.The many alcohol of aliphatic polycarbonate that the present invention adopts comprise the carbonate group that has flame retardancy in a large number, carbonate group mass contg warp
1H NMR spectrogram method is measured, and molar fraction reaches 0.2-0.5, and oxygen-consumption is little when having burning, the characteristics that the combustion heat is low.As the how pure combustion heat of poly (propylene carbonate) is 4420kcal/kg, polymerized thylene carbonate second ester polyol is 3326kcal/kg, and the combustion heat with many alcohol of poly(propylene oxide) of similar structures is 7748kcal/kg, the combustion heat of the many alcohol of polyethylene oxide is 6637kcal/kg, polyethylene is 11242kcal/kg, about polyethers that the many pure combustions heat of aliphatic polycarbonate of the present invention only are similar structures and half of the polyester polyol combustion heat, carbonate group mass contg (% in the synthetic polyurethane foamed material thus, w) between 15%～30%, high carbon acid ester group content makes it compare with the polyether(poly)urethane foam materials with polyester type commonly used, has the low combustion heat, the characteristics of high flame retardant.
Provided by the invention is that starting raw material synthetic Aliphatic Polycarbonate Polyurethanes foam is compared with general purpose polyester type and polyether-type foam with the carbonic acid gas, has good low temperature kindliness and wear resistance simultaneously.Contain a large amount of ehter bonds in the many alcohol resins of aliphatic polycarbonate that the present invention adopts, the existence of diether linkage structure makes polymkeric substance have the submissive performance of good low temperature.Simultaneously, these many alcohol also contain a large amount of ester bonds, and the existence of ester bond makes polymkeric substance have good wear resistance.
Also has good biodegradation type according to method synthetic polymerized thylene carbonate ethyl ester type polyurethane provided by the present invention.This polyurethane foam can be used for the place of the disposable application of requirement, as disposable lunch box, non-returnable container material etc.
Adopting method synthetic Aliphatic Polycarbonate Polyurethanes foam of the present invention to have high carbon acid ester group concentration characteristics, is 25% as carbonate group mass contg in the polycarbonate polyurethane foam of the method preparation of adopting embodiment 8.
In addition, adopt method synthetic Aliphatic Polycarbonate Polyurethanes foam of the present invention also to have low density, high-intensity characteristics, as the synthetic Aliphatic Polycarbonate Polyurethanes foamy structure that obtains of the method that adopts embodiment 2 belongs to semihard bubble category, its tensile strength is 0.27MPa, 40% compressive hardness is 0.13MPa, and the tensile strength with universal semihard bubble of equal densities is 013-0.17MPa, and 40% compressive hardness is 0.014-0.018MPa.
That the present invention can be widely used in is soft, the production of semi-rigid and hard butter adoption carbonic ether urethane foam.The present invention is particularly useful for step foaming, a semi-prepolymer method, prepolymer method and prepares soft, semi-rigid and hard butter adoption carbonic ether urethane foam.
Can be used for aspects such as mattress, furniture, carpet according to method synthetic flexible PU foam provided by the present invention.Can be used for automotive material, building structural materials, thermal insulation material, wrapping material and polyurethane sole materials etc. according to method synthetic hard provided by the present invention, semi-rigid foamed plastics.
Have good degradation property according to some kind polyurethane foam of method synthetic provided by the present invention, can be used for the place of the disposable application of requirement, as disposable lunch box, non-returnable container material etc.
The basic step that is generally used for preparing the Aliphatic Polycarbonate Polyurethanes porous plastics of assessing porous plastics performance and the application of preparation experiment chamber is as follows:
1,, adopt powerful whipping appts (rotating speed 2000rpm) fully evenly mixed with in used system component scale to a proper container.
2, reaction mixture is poured in 20 * 30 * 10 the constant temperature mould (die temperature is at 40 ℃) into free foaming.
3, treat that polymer foaming finishes the back self-vulcanizing demoulding in 48 hours and gets final product.
Preferred forms
The urethane foam that the present invention relates to can be synthetic by following method, but claim of the present invention is not limited.
Embodiment 1
50 gram dipropylene glycol, 500 milliliters of toluene, 2000 milliliters of propylene oxide, 20 gram macromolecule loading double metal cyanides (ZL 89100701) are added in 5 liters of reactors as catalyzer, and normal temperature stirred 15 minutes down, added 1100 gram carbonic acid gas then.Open to stir and heating unit in 60 ℃ of reactions 6 hours down, be cooled to room temperature, discharging behind residual epoxy propane and the solvent is taken off in decompression.
Get the 1000g polymerisate and add 2000 milliliters of boiling water, stirred 15 minutes, resin layer is transferred in the there-necked flask of 2000ml, vacuum hydro-extraction discharging after about 3 hours under 60 ℃, whipped state, measure expect in moisture content (Fei Xiufa measurement), polymericular weight.Polymericular weight adopts viscosimetry to measure, according to document (Chen Liban, Ni's flaw, Yang Shuying, Deng. from the novel method of GPC and the various average molecular mass of intrinsic viscosity calculating superpolymer. the analytical test journal, 1995,3:24-28) calculating the polymkeric substance number-average molecular weight is 3700, calculate polymkeric substance hydroxyl value 0.00054mol/g in conjunction with hydroxy functionality, adopt
1HNMR determines carbonate group mass contg (mole) 0.37 in the resin.
Get 100g dehydration back resin in the beaker of 250ml, add the water miscible polyether silicone of 1g (suds-stabilizing agent), 1.6g water (add and do not remove amount of moisture in the polymkeric substance fully), the 6g glycerol, 0.04g the dipropylene glycol solution of 6.4% di-n-butyltin dilaurate, 0.06g 0.33% triethylene diamine dipropylene glycol solution, adopt powerful whipping appts to stir (agitator speed 2000rmp), treat that fully mixed evenly back adds 65.8g carbonization two inferior acid amides modification MDI (MDI index 1.1), stir mixed, pour in the foaming mould fast evenly, free foaming solidifies the demoulding after 48 hours.
Sample after the above-mentioned demoulding is measured its physicals as follows:
Foam density: GB-6343-86
Tensile strength: GB-6344-86
Elongation: GB-6344-86
Compressive strength, modulus of compression: GB-8812-88
Flexural strength modulus in flexure: GB-9341-88
According to embodiment 1 resulting polyurethane foam physicals such as table 1.
Embodiment 2
Get 100g by the resin (dehydration back) of embodiment 1 method preparation in the beaker of 250ml, add the water miscible polyether silicone of 1g (suds-stabilizing agent), 2.6g water (add and do not remove amount of moisture in the polymkeric substance fully), the 6g glycerol, 0.04g the dipropylene glycol solution of 6.4% di-n-butyltin dilaurate, 0.06g33% triethylene diamine dipropylene glycol solution, adopt powerful whipping appts to stir (agitator speed 2000rmp), treat that fully mixed evenly back adds 83.0g carbonization two inferior acid amides modification MDI (MDI index 1.1), stir mixed, pour in the foaming mould fast evenly, free foaming solidifies the demoulding after 48 hours.
The product physicals is pressed embodiment 1 method and is measured, result such as table 1.
Embodiment 3
Get 100g by the resin (dehydration back) of embodiment 1 method preparation in the beaker of 250ml, add the water miscible polyether silicone of 1g (suds-stabilizing agent), 2.6g water (add and do not remove amount of moisture in the polymkeric substance fully), the 3g glycerol, the dipropylene glycol solution of the di-n-butyltin dilaurate of 0.04g6.4%, 0.06g33% triethylene diamine dipropylene glycol solution, adopt powerful whipping appts to stir (agitator speed 2000rmp), treat that fully mixed evenly back adds 67.9g carbonization two inferior acid amides modification MDI (MDI index 1.1), stir mixed, pour in the foaming mould fast evenly, free foaming solidifies the demoulding after 48 hours.
The product physicals is pressed embodiment 1 method and is measured, result such as table 1.
Embodiment 4
70 gram dipropylene glycol, 500 milliliters of toluene, 2000 milliliters of propylene oxide, 20 gram macromolecule loading double metal cyanides (ZL 89100701) are added in 5 liters of reactors as catalyzer, and normal temperature stirred 25 minutes down, added 1100 gram carbonic acid gas then.Method by embodiment 1 is prepared, and the molecular weight that obtains many alcohol resins is 2200, and carbonate group mass contg (mole) is 0.34 in the how pure molecule.
Get 100g resin (dehydration back), according to the method free foaming of embodiment 1 (the MDI index is 1.1).It is as shown in table 1 to obtain foaming properties.
Embodiment 5
40 gram dipropylene glycol, 500 milliliters of toluene, 2000 milliliters of propylene oxide, 20 gram macromolecule loading double metal cyanides (ZL 89100701) are added in 5 liters of reactors as catalyzer, and normal temperature stirred 30 minutes down, added 1100 gram carbonic acid gas then.Method by embodiment 1 is prepared, and the molecular weight that obtains many alcohol resins is 4500, and carbonate group mass contg (mole) is 0.34 in the how pure molecule.
Get 100g resin (dehydration back), according to the method free foaming of embodiment 1 (the MDI index is 1.1).It is as shown in table 1 to obtain foaming properties.
Embodiment 6
With 400 gram molecular weights, 400 hydroxy functionalities is that 3 polyether polyol, 2500 milliliters of propylene oxide, 20 gram macromolecule loading double metal cyanides (ZL 89100701) add in 5 liters of reactors as catalyzer, normal temperature stirred 20 minutes down, added 1100 gram carbonic acid gas then.Method by embodiment 1 is prepared, and the molecular weight that obtains many alcohol resins is 2100, and carbonate group mass contg (mole) is 0.23 in the how pure molecule.
Get 100g resin (dehydration back), according to the method free foaming of embodiment 1 (the MDI index is 1.1).It is as shown in table 1 to obtain foaming properties.
Embodiment 7
70 gram dipropylene glycol, 2500 milliliters of oxyethane, 20 gram PBM catalyzer are added in 5 liters of reactors, and normal temperature stirred 15-30 minute down, added 1100 gram carbonic acid gas then.Method by embodiment 1 is prepared, and the molecular weight that obtains many alcohol resins is 3200, and carbonate group mass contg (mole) is 0.39 in the how pure molecule.
Get 100g resin (dehydration back), according to the method free foaming of embodiment 1 (the MDI index is 1.1).It is as shown in table 1 to obtain foaming properties.
Embodiment 8
70 gram dipropylene glycol, 2000 milliliters of oxyethane, 20 gram macromolecule loading double metal cyanides (ZL89100701) are added in 5 liters of reactors as catalyzer, and normal temperature stirred 20 minutes down, added 1500 gram carbonic acid gas then.Method by embodiment 1 is prepared, and the molecular weight that obtains many alcohol resins is 1760, and carbonate group mass contg (mole) is 0.43 in the how pure molecule.
Get 100g resin (dehydration back), according to the method free foaming of embodiment 1 (the MDI index is 1.1).It is as shown in table 1 to obtain foaming properties.
Table 1 urethane foam physicals
Close tension fracture elasticity 40% bending compression bending
Performance degree intensity modulus of stretch compressive hardness modulus intensity modulus
Kg/m3 MPa leads % MPa Mpa MPa Mpa Mpa
Embodiment 1 114.8 0.60 17.2 7.79 0.615 24.6 0.67 9.83
Embodiment 2 55.9 0.27 50.6 2.72 0.13 5.15 0.180 3.93
Embodiment 3 42.4 0.23 33.67 1.42 0.105 4.06 0.167 2.98
Embodiment 4 53.8 0.26 20.1 2.66 0.12 4.31 0.262 4.05
Embodiment 5 49.1 0.25-2.24 0.13-0.223 4.03
Embodiment 6 53.8 0.26 20.1 2.66 0.12 4.31 0.262 4.05
Embodiment 7 49.1 0.25-2.24 0.13-0.223 4.03
Embodiment 8 51 0.28-2.45 0.15-0.244 4.15
Claims (10)
1, a kind of with carbonic acid gas as starting raw material synthetic aliphatic polycarbonate type polyurethane foam materials, be by many alcohol of aliphatic polycarbonate and vulcabond and/or the polymeric isocyanate of isocyanate index between 60-200, at catalyzer, whipping agent, crosslinked or chainextender, the existence of suds-stabilizing agent and other auxiliary agents is the reaction synthetic down, the many alcohol of wherein said aliphatic polycarbonate are to adopt carbonic acid gas and epoxide synthetic, number-average molecular weight is no more than 10000, hydroxy functionality is 2,3 or higher, the molar fraction of carbonate group is between 0.2～0.5 in the molecule; The polyurethane foamed material carbonate group mass contg that makes is between 15～30wt%.
2, a kind of method for preparing the type polyurethane of aliphatic polycarbonate described in the claim 1 foam materials, be to adopt carbonic acid gas and epoxide to be no more than 10000 by molecular weight regulator synthetic number-average molecular weight, hydroxy functionality is 2,3 or higher, how pure the aliphatic polycarbonate of the molar fraction of carbonate group between 0.2～0.5 be in the molecule; Again by many alcohol of described aliphatic polycarbonate and vulcabond and/or the polymeric isocyanate of isocyanate index between 60-200, in the presence of catalyzer, whipping agent, crosslinked or chainextender, suds-stabilizing agent and other auxiliary agents, react synthetic.
3,, it is characterized in that described epoxide is selected from one or several the miscellany in oxyethane, propylene oxide and the butylene oxide ring according to the method described in the claim 2.
4,, it is characterized in that described molecular weight regulator is selected from one or several the mixture in the aliphatics of hydroxy functionality 〉=2 or the many alcohol of aromatic series, polyphenol, low-molecular-weight polyether polyol, polyester polyol, the many alcohol of aliphatic polycarbonate etc. according to the method described in claim 2 or 3.
5, according to the method described in claim 2 or 3, the molar fraction that it is characterized in that carbonic ether in the many alcohol of described aliphatic polycarbonate is between 0.20-0.45, and number-average molecular weight is between the 500-5000.
6,, it is characterized in that the many alcohol of described aliphatic polycarbonate are selected from aliphatic poly polypropylene carbonate ester polyol, how pure the aliphatic poly ethylene carbonate is according to the method described in claim 2 or 3.
7, according to the method described in claim 2 or 3, it is characterized in that described vulcabond and polymeric isocyanate are selected from tolylene diisocyanate, 1,6-hexylidene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, carbodiimide modified diphenylmethane diisocyanate, poly isocyanate.
8, it is according to the method described in claim 2 or 3, it is characterized in that described catalyzer is selected from tin class catalyzer di-n-butyltin dilaurate, stannous octoate and tertiary amine catalyst triethylenediamine, N, the N`-dimethylcyclohexylamine, two-(2-dimethylaminoethyl) ether, N`-methyl-N` (2-dimethylamino) ethyl piperazidine, N, N, N`, N`-tetramethyl--1, the 6-butanediamine, N, the N-dimethylaminoethanol, N, N, N`, N`, N`-five methyl diethylentriamine, N, N`, N`, N`-tetramethylethylened, trolamine, described catalyst consumption is alcohol resin more than 0.001-0.5 part/100 part by weight.
9, according to the method described in claim 2 or 3, it is characterized in that described linking agent and chainextender are small-molecule substance, its molecule contain can with the reactive hydrogen of isocyanate reaction, and its molecular weight is below 500 usually, the reactive hydrogen number is between 2-12 in the molecule.
10, according to the method described in claim 2 or 3, it is characterized in that described suds-stabilizing agent is selected from contains sulfonic tensio-active agent, water miscible polyether silicone, and its consumption is alcohol resin more than 0.1-6 part/100 part by weight.
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| KR101455878B1 (en) | 2006-11-15 | 2014-11-03 | 바스프 에스이 | Process for producing flexible polyurethane foams |
| CN101857670B (en) | 2009-04-10 | 2013-04-03 | 拜耳材料科技(中国)有限公司 | Polyurethane microporous elastomer, preparation method and application thereof |
| CN101597376B (en) * | 2009-07-10 | 2011-08-10 | 中山大学 | Polyurethane propylene carbonate material and preparation method thereof |
| CN102010650B (en) * | 2010-11-30 | 2012-11-07 | 江门市德商科佐科技实业有限公司 | Waterborne polyurethane coating and preparation method thereof |
| CN102093535B (en) * | 2010-12-23 | 2013-05-01 | 上海凯众聚氨酯有限公司 | Method for preparing microporous polyurethane elastomer |
| CN102140158B (en) * | 2010-12-30 | 2012-12-26 | 江门市德商科佐科技实业有限公司 | Polyurethane material based on carbon dioxide copolymer polyalcohol and application thereof |
| CN102093701B (en) * | 2010-12-31 | 2012-11-28 | 广东达志环保科技股份有限公司 | Sports field poly(ethylene carbonate) polyurethane paving material and preparation method thereof |
| CN102241942B (en) * | 2011-06-30 | 2013-06-19 | 江苏中科金龙化工有限公司 | Poly(propylene carbonate)-based polyurethane fireproof coating and preparation method thereof |
| EP2838954A4 (en) * | 2012-04-16 | 2015-11-25 | Novomer Inc | Adhesive compositions and methods |
| CN109021209A (en) * | 2012-11-07 | 2018-12-18 | 沙特阿美技术公司 | High-strength polyurethane foam compositions and method |
| CN104277194B (en) | 2013-07-05 | 2018-11-30 | 科思创德国股份有限公司 | Polyurethane resin composition and polyurethane composition prepared therefrom |
| CN104177805B (en) * | 2014-09-04 | 2016-06-01 | 中国科学院长春应用化学研究所 | The blend of carbon dioxide-epoxy propane copolymer and its preparation method |
| CN105331087B (en) * | 2015-11-13 | 2017-12-01 | 吴江市风尚鞋厂 | A kind of footwear material of wear-resisting high-strength degree and preparation method thereof |
| CN105482149B (en) * | 2015-12-10 | 2018-10-26 | 深圳乐活园艺生态技术有限公司 | Whole ventilating plantation sponge of controllable biodegradable and preparation method thereof |
| CN105524244B (en) * | 2016-02-25 | 2018-05-18 | 林家豪 | A kind of manufacturing method of compound polyurethane material for footwear material |
| FR3054237B1 (en) * | 2016-07-25 | 2020-06-12 | Centre National De La Recherche Scientifique - Cnrs | REDUCTION KIT, REDUCING COMPOSITION AND THEIR USE |
| CN110511714B (en) * | 2017-11-14 | 2021-07-30 | 广元瑞峰新材料有限公司 | Polyurethane fireproof adhesive for building |
| US20200339732A1 (en) * | 2017-12-21 | 2020-10-29 | Econic Technologies Ltd | Rigid foams |
| CN110964167A (en) * | 2018-09-29 | 2020-04-07 | 青岛科技大学 | Preparation method of polyester type polyurethane foam |
| CN113429538B (en) * | 2021-07-20 | 2022-04-05 | 揭阳市宏信塑胶制品有限公司 | Foam plastic with antibacterial and mildewproof functions |
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