CN103665308B - Elastomerics and carbon dioxide-epoxy propane copolymer porous plastics - Google Patents
Elastomerics and carbon dioxide-epoxy propane copolymer porous plastics Download PDFInfo
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Abstract
The present invention provides elastomerics and carbon dioxide-epoxy propane copolymer porous plastics, and this carbon dioxide-epoxy propane copolymer porous plastics comprises carbon dioxide-epoxy propane copolymer, elastomerics, poly-hexanodioic acid/butylene terephthalate, whipping agent. Compared with existing carbon dioxide-epoxy propane copolymer porous plastics, the present invention all adopts and the raw material of biological degradation can prepare carbon dioxide-epoxy propane copolymer porous plastics, wherein, adding of elastomerics, the toughness of porous plastics can not only be improved, and carbon dioxide-epoxy propane copolymer and the consistency of poly-hexanodioic acid/butylene terephthalate can be improved; And gather adding of hexanodioic acid/butylene terephthalate, further increase the toughness of carbon dioxide-epoxy propane copolymer porous plastics, therefore carbon dioxide-epoxy propane copolymer porous plastics provided by the invention not only can biological degradation, and there is good mechanical property, there is compressible and feature that is reversibility.
Description
Technical field
The invention belongs to Biodegradable foam plastic technical field, particularly relate to elastomerics and carbon dioxide-epoxy propane copolymer porous plastics.
Background technology
In the prior art, the porous plastics such as polyolefins plastic foam material, polyurethanes plastic foam material are owing to having the advantage of light weight, heat insulation, sound-absorbing, damping, it is widely used as the functional materials such as thermal insulation material, sound-proof material, also can be used as preparing the case material of the transportation means such as car, ship simultaneously. But, these plastic foam light weight, mention fluffy when discarded, therefore, it is difficult to recycling, in addition, even these porous plastics are buried or burned, also will be polluted by environment.
Degradable high polymer material is used to be one of effective way reducing conventional plastic pollution. Prior art discloses multiple Biodegradable foam plastic, the Chinese patent being CN1596279A such as publication number discloses a kind of foaming sheet adopting the Biodegradable resins such as poly(lactic acid), biological degradability condensation polymer type aliphatic polyester or lactone resin to prepare as major ingredient; The Chinese patent that publication number is CN101747605A discloses a kind of foam materials adopting poly (hydroxyalkanoate) ester to prepare as major ingredient; Publication number be CN102051031A Chinese patent disclosed in foam material there is good toughness also there is excellent elasticity and wear resistance, described Biodegradable resin is any one or more than two kinds compositions in PHAs, PBS, PCL; The Chinese patent of publication number to be CN101899200A and publication number be CN102627837A discloses the preparation method of biodegradable poly butylene succinate (PBS) foam materials.
Carbon dioxide-epoxy propane copolymer porous plastics also has the advantage of environmental protection, carbonic acid gas can be fixed by it on the one hand, alleviation is by the shortage of industrial chemicals, on the other hand, the complete biodegradable characteristic of carbon dioxide-epoxy propane copolymer is utilized can effectively to solve the problem of environmental pollution of foam waste initiation, therefore, carbon dioxide-epoxy propane copolymer porous plastics is subject to the people's attention.
Application number be 201210284926.9 Chinese patents disclose a kind of can the carbon dioxide-epoxy propane copolymer porous plastics of biological degradation and its preparation method, using carbon dioxide-epoxy propane copolymer as raw material, water is as whipping agent, select suitable water carrier, directly extrude after carbon dioxide-epoxy propane copolymer, water and water carrier are mixed, obtain carbon dioxide-epoxy propane copolymer porous plastics. Porous plastics prepared by the method has the high advantage of expansion ratio, but the rebound performance of gained porous plastics is poor, limits its application.
Application number be 201310275682.2 Chinese patent disclose a kind of carbon dioxide-epoxy propane copolymer porous plastics and its preparation method, using carbon dioxide-epoxy propane copolymer as raw material, by the method for chemistry moulded from foam, obtain carbon dioxide-epoxy propane copolymer porous plastics. Porous plastics prepared by the method has good rebound resilience, but can not the elastic body toughening foam of biological degradation owing to wherein adding so that this porous plastics not can complete biodegradable, limit its application.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide elastomerics and carbon dioxide-epoxy propane copolymer porous plastics, and this carbon dioxide-epoxy propane copolymer porous plastics can completely be degraded and be had good mechanical property.
The present invention provides a kind of elastomerics, obtains through alcohol compound chain extension by after poly-(carbonic ether-ether) dibasic alcohol and/or poly-(carbonic ether-ether) polyvalent alcohol and diisocyanate compound reaction; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
Preferably, described diisocyanate compound is selected from hexamethylene diisocyanate, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4, one or more in the dimer of 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, tolylene diisocyanate and the tripolymer of 4,4 '-diphenylmethanediisocyanate.
Preferably, described alcohol compound is selected from 1,4-butyleneglycol, ethylene glycol, 1,2-propylene glycol, 1, one or more in ammediol, hexylene glycol, glycol ether, 1,8-ethohexadiol, 1,4-cyclohexanediol, diethanolamine, trolamine, TriMethylolPropane(TMP) and glycerol.
Present invention also offers a kind of method for producing elastomers, comprise the following steps:
S1) (carbonic ether-ether) dibasic alcohol will be gathered and/or gather (carbonic ether-ether) polyvalent alcohol and mix with diisocyanate compound, and react under protection of inert gas, obtain prepolymer;
S2) described prepolymer is mixed with alcohol compound, react under protection of inert gas, obtain elastomerics; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
Preferably, described poly-(carbonic ether-ether) dibasic alcohol and/or poly-(carbonic ether-ether) polyvalent alcohol are 1:(0.98��1.2 with diisocyanate compound according to hydroxyl and isocyano mol ratio) ratio mix.
Present invention also offers a kind of carbon dioxide-epoxy propane copolymer porous plastics, comprising:
Preferably, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 80000��200000g/mol.
Preferably, the molecular weight distribution of described carbon dioxide-epoxy propane copolymer is 1.5��7.0.
Preferably, described whipping agent is sulfohydrazide type blowing agent and/or azo foaming agent.
Present invention also offers the preparation method of a kind of carbon dioxide-epoxy propane copolymer porous plastics, comprise the following steps:
After the whipping agent melting mixing of the poly-hexanodioic acid/butylene terephthalate of the elastomerics of the carbon dioxide-epoxy propane copolymer of 100 weight parts, 5��50 weight parts, 50��200 weight parts and 2��15 weight parts, carry out suppressing, moulded from foam, obtain carbon dioxide-epoxy propane copolymer porous plastics; Described elastomerics is the elastomerics described in claims 1 to 3 any one or the elastomerics prepared by claim 4��5 any one.
The present invention provides elastomerics and carbon dioxide-epoxy propane copolymer porous plastics, and this carbon dioxide-epoxy propane copolymer porous plastics comprises 100 weight part carbon dioxide-epoxy propane copolymers, 5��50 weight parts of elastomer, 50��200 weight parts poly-hexanodioic acid/butylene terephthalate, 2��15 parts by weight of blowing agent. Compared with existing carbon dioxide-epoxy propane copolymer porous plastics, the present invention all adopts and the raw material of biological degradation can prepare carbon dioxide-epoxy propane copolymer porous plastics, wherein, adding of elastomerics, the toughness of carbon dioxide-epoxy propane copolymer porous plastics can not only be improved, and carbon dioxide-epoxy propane copolymer and the consistency of poly-hexanodioic acid/butylene terephthalate can be improved; And gather adding of hexanodioic acid/butylene terephthalate, further improve the toughness of carbon dioxide-epoxy propane copolymer porous plastics, therefore carbon dioxide-epoxy propane copolymer porous plastics provided by the invention not only can biological degradation, and there is good mechanical property, there is compressible and feature that is reversibility.
Experimental result shows, the tensile strength of carbon dioxide-epoxy propane copolymer porous plastics prepared by the present invention is 220��270Kpa, and elongation at break is 9%��13%, and compressive strength is 21��26Kpa.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the carbon dioxide-epoxy propane copolymer porous plastics that the embodiment of the present invention 1 prepares.
Embodiment
The present invention provides a kind of elastomerics, obtains through alcohol compound chain extension by after poly-(carbonic ether-ether) dibasic alcohol and/or poly-(carbonic ether-ether) polyvalent alcohol and diisocyanate compound reaction; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
The restriction that the present invention is not special to the source of all raw materials, for commercially available.
Wherein, described poly-(carbonic ether-ether) dibasic alcohol and poly-(carbonic ether-ether) polyvalent alcohol are poly-(carbonic ether-ether) dibasic alcohol well known to those skilled in the art and poly-(carbonic ether-ether) polyvalent alcohol, there is no special restriction.
Described diisocyanate compound can be the diisocyanate compound that aliphatic diisocyanate compound also can be non-fat race, there is no special restriction, the present invention is preferably selected from hexamethylene diisocyanate, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4, one or more in the dimer of 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, tolylene diisocyanate and the tripolymer of 4,4 '-diphenylmethanediisocyanate.
Described alcohol compound is dibasic alcohol well known to those skilled in the art and/or polyvalent alcohol, there is no special restriction. The present invention is preferably 1,4-butyleneglycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, hexylene glycol, glycol ether, 1, one or more in 8-ethohexadiol, 1,4-cyclohexanediol, diethanolamine, trolamine, TriMethylolPropane(TMP) and glycerol.
Present invention also offers a kind of above-mentioned method for producing elastomers, comprise the following steps: S1) (carbonic ether-ether) dibasic alcohol will be gathered and/or poly-(carbonic ether-ether) polyvalent alcohol mixes with diisocyanate compound, react under protection of inert gas, obtain prepolymer; S2) described prepolymer is mixed with alcohol compound, react under protection of inert gas, obtain elastomerics; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
Wherein, described poly-(carbonic ether-ether) dibasic alcohol and poly-(carbonic ether-ether) polyvalent alcohol are preferably prepared according to the Chinese patent of the Chinese patent of publication number to be the Chinese patent of CN102432857A, publication number be CN102617844A, publication number to be the Chinese patent of CN1060299A and publication number be CN102206333A, also can according to document JournalofPolymerResearch, 2012, prepared by 19:9878 and JournalofPolymerSciencePartA:PolymerChemistry2012,50:517 7.
Described diisocyanate compound and alcohol compound are all same as above, do not repeat them here.
(carbonic ether-ether) dibasic alcohol will be gathered and/or gather (carbonic ether-ether) polyvalent alcohol and mix with diisocyanate compound, be preferably 1:(0.98��1.2 according to hydroxyl and isocyano mol ratio) ratio add, it is more preferable to according to 1:(1��1.05) ratio add.
(carbonic ether-ether) dibasic alcohol will be gathered and/or gather (carbonic ether-ether) polyvalent alcohol and mix with diisocyanate compound, and react under protection of inert gas, obtain prepolymer. Wherein, described rare gas element is shielding gas well known to those skilled in the art, there is no special restriction, is preferably nitrogen in the present invention; The temperature of reaction of this reaction is preferably 70 DEG C��100 DEG C, it is more preferable to be 75 DEG C��90 DEG C; The time of described reaction is preferably 6��10h, it is more preferable to be 7��9h.
Described prepolymer is mixed with alcohol compound, reacts under protection of inert gas, obtain elastomerics. The addition of described alcohol compound is preferably poly-(carbonic ether-ether) dibasic alcohol and/or gathers the 0.3%��5% of (carbonic ether-ether) polyvalent alcohol and diisocyanate compound total mass, it is more preferable to be 1%��4%; In this step, the temperature of reaction is preferably 50 DEG C��80 DEG C, it is more preferable to be 55 DEG C��65 DEG C; The time of this reaction is preferably 3��6h, it is more preferable to be 4��5h.
The effect of alcohol compound is that prepolymer is carried out chain extension, be on the one hand due to alcohol compound can with excessive isocyanate reaction, the chain extension of alcohol compound can make molecular weight of product be increased exponentially on the other hand, it is possible to the mechanical property of elastomerics is greatly enhanced.
Present invention also offers a kind of carbon dioxide-epoxy propane copolymer porous plastics comprising above-mentioned elastomerics, comprising:
Described carbon dioxide-epoxy propane copolymer is carbon dioxide-epoxy propane copolymer well known to those skilled in the art, there is no special restriction, in the present invention, its molecular weight is preferably 80000��200000g/mol, it is more preferable to be 100000��180000g/mol; The molecular weight distribution of described carbon dioxide-epoxy propane copolymer is preferably 1.5��7, it is more preferable to be 2.5��5.
Described elastomerics is same as above, does not repeat them here. In carbon dioxide-epoxy propane copolymer porous plastics of the present invention, the content of this elastomerics is preferably 10��30 weight parts. Elastomerics can not only improve the toughness of carbon dioxide-epoxy propane copolymer porous plastics, but also can improve carbon dioxide-epoxy propane copolymer and the consistency of poly-hexanodioic acid/butylene terephthalate.
Described poly-hexanodioic acid/butylene terephthalate is poly-hexanodioic acid/butylene terephthalate well known to those skilled in the art, there is no special restriction. In carbon dioxide-epoxy propane copolymer porous plastics of the present invention, its content is preferably 80��150 weight parts, it is more preferable to be 80��100 weight parts. Poly-hexanodioic acid/butylene terephthalate can improve the toughness of carbon dioxide-epoxy propane copolymer porous plastics.
The content of described whipping agent is preferably 5��10 weight parts; Whipping agent described in the present invention is preferably sulfohydrazide type blowing agent and/or azo foaming agent, it is more preferable to be Cellmic C 121. In addition, owing to its thermal decomposition rate is had a certain impact by the particle diameter of whipping agent, when the particle diameter of whipping agent diminishes, the thermal decomposition rate of whipping agent becomes fast, and bubble becomes big; When the particle diameter of whipping agent becomes big, thermal decomposition rate becomes slow, bubble diminishes. Steeping uniformly to obtain bubble, the median size of whipping agent described in the present invention is preferably 3��30 ��m, it is more preferable to be 5��28 ��m.
According to the present invention, described carbon dioxide-epoxy propane copolymer porous plastics preferably also comprises additives for plastics. Additives for plastics can make carbon dioxide-epoxy propane copolymer porous plastics while having better mechanical property, additionally it is possible to other performances required for meeting it. In the present invention, described additives for plastics be preferably in oxidation inhibitor, lubricant, pigment, weighting agent and bubble stabilizer one or more, described additives for plastics can be selected by those skilled in the art according to the performance of desired product.
Wherein, described oxidation inhibitor can improve the aging resistance of carbon dioxide-epoxy propane copolymer porous plastics. In the present invention, the kind of described oxidation inhibitor is preferably antioxidant 1010 and/or oxidation inhibitor 626; The consumption of described oxidation inhibitor is not had special restriction by the present invention, adopts the addition in porous plastics of those skilled in the art's resin.
Lubricant can improve the processing characteristics of carbon dioxide-epoxy propane copolymer porous plastics. Lubricant described in the present invention be preferably in stearic acid, glyceryl monostearate and whiteruss one or more, it is more preferable to be stearic acid; Taking the carbon dioxide-epoxy propane copolymer of 100 weight parts as benchmark, the content of described lubricant is preferably 0.07��0.13 weight part, it is more preferable to be 0.09��0.11 weight part, then is preferably 0.1 weight part.
Pigment can change the color of carbon dioxide-epoxy propane copolymer porous plastics. The pigment added in the present invention is preferably the conventional toner of plastics; Taking the carbon dioxide-epoxy propane copolymer of 100 weight parts as benchmark, described pigment is preferably 0.0005��0.0013 weight part, it is more preferable to be 0.0008��0.0011 weight part, then is preferably 0.001 weight part.
Weighting agent can reduce the cost of carbon dioxide-epoxy propane copolymer porous plastics of the present invention. According to the present invention, described weighting agent is preferably calcium carbonate and/or talcum powder, it is more preferable to be calcium carbonate; Taking the carbon dioxide-epoxy propane copolymer of 100 weight parts as benchmark, described weighting agent is preferably 5��15 weight parts, it is more preferable to be 8��12 weight parts.
Bubble stabilizer can improve the processing characteristics of carbon dioxide-epoxy propane copolymer porous plastics. According to the present invention, described bubble stabilizer be preferably in silicone oil, carbonic ether coupling agent, silane coupling agent, aluminate coupling agent, Trisodium Citrate, sodium sorbate and sodium lauryl sulphate one or more, it is more preferable to be silicone oil; Taking the carbon dioxide-epoxy propane copolymer of 100 weight parts as benchmark, described bubble stabilizer is preferably 0.07��0.13 weight part, it is more preferable to be 0.09��0.11 weight part, then is preferably 0.1 weight part.
The present invention all adopts and the raw material of biological degradation can prepare carbon dioxide-epoxy propane copolymer porous plastics, wherein, adding of elastomerics, the toughness of carbon dioxide-epoxy propane copolymer porous plastics can not only be improved, and carbon dioxide-epoxy propane copolymer and the consistency of poly-hexanodioic acid/butylene terephthalate can be improved; And gather adding of hexanodioic acid/butylene terephthalate, further improve the toughness of carbon dioxide-epoxy propane copolymer porous plastics, therefore carbon dioxide-epoxy propane copolymer porous plastics provided by the invention not only can biological degradation, and there is good mechanical property, there is compressible and feature that is reversibility.
Present invention also offers the preparation method of a kind of above-mentioned carbon dioxide-epoxy propane copolymer porous plastics, comprise the following steps: after the whipping agent melting mixing of the poly-hexanodioic acid/butylene terephthalate of the elastomerics of the carbon dioxide-epoxy propane copolymer of 100 weight parts, 5��50 weight parts, 50��200 weight parts and 2��15 weight parts, carry out suppressing, moulded from foam, obtain carbon dioxide-epoxy propane copolymer porous plastics.
Wherein, described carbon dioxide-epoxy propane copolymer, elastomerics, poly-hexanodioic acid/butylene terephthalate and whipping agent, all with upper described identical, do not repeat them here.
According to the present invention, described carbon dioxide-epoxy propane copolymer becomes to obtain with epoxypropane copolymerization by carbonic acid gas, is the plastics of a kind of amorphous biodegradable. the restriction that the present invention is not special to the source of described carbon dioxide-epoxy propane copolymer, can obtain by market is bought, also can prepare according to the preparation method of carbon dioxide-epoxy propane copolymer disclosed in prior art well known to those skilled in the art, as publication number can be adopted to be CN1257885, disclosed in the Chinese patent of CN1436803 and CN1257753, the preparation method of polycarbonate prepares carbon dioxide-epoxy propane copolymer, can also be prepared in accordance with the following methods: by carbonic acid gas and propylene oxide under the katalysis of trichoroacetic acid(TCA) yttrium-ethyl zinc-glycerol composition catalyzer, carry out copolyreaction, obtain carbon dioxide-epoxy propane copolymer.
Trichoroacetic acid(TCA) yttrium-ethyl zinc-glycerol composition catalyzer is preferably introduced in the reactor of full carbonic acid gas by the present invention under anaerobic, then adds propylene oxide wherein, carries out copolyreaction, obtains carbon dioxide-epoxy propane copolymer.
The quality of described trichoroacetic acid(TCA) yttrium-ethyl zinc-glycerol composition catalyzer and propylene oxide is not had special restriction by the present invention, adopts the consumption preparing catalyzer that carbon dioxide-epoxy propane copolymer adopts and propylene oxide well known to those skilled in the art; The pressure of described carbonic acid gas and propylene oxide copolyreaction is preferably 3.0��4.0MPa, it is more preferable to be 3.5MPa; The temperature of described copolyreaction is preferably 50 DEG C��70 DEG C, it is more preferable to be 55 DEG C��65 DEG C, then is preferably 60 DEG C; The time of described copolyreaction is preferably 10��15h, it is more preferable to be 12h.
After completing above-mentioned copolyreaction, it is preferable that add methanol hydrochloride solution termination reaction in the reaction solution of above-mentioned copolyreaction, then the reaction product obtained is washed, obtain carbon dioxide-epoxy propane copolymer. The methanol hydrochloride solution that termination reaction is adopted by the present invention does not have special restriction, is methanol hydrochloride solution well known to those skilled in the art, and in the present invention, the massfraction of described methanol hydrochloride solution is preferably 5%; The method of described washing is not had special requirement by the present invention, adopts the technical scheme of washing well known to those skilled in the art, it is preferred to use methyl alcohol washs.
By the whipping agent melting mixing of the poly-hexanodioic acid/butylene terephthalate of the elastomerics of the carbon dioxide-epoxy propane copolymer of 100 weight parts, 5��50 weight parts, 50��200 weight parts and 2��15 weight parts, preferably first above-mentioned raw materials is stirred after evenly, then carry out melting mixing; The uniform method of described stirring is the uniform method of stirring well known to those skilled in the art, there is no special restriction, and the present invention preferably carries out stirring evenly in stirrer or mixing machine; The method of melting mixing of the present invention does not have special restriction, is the method for melting mixing well known to those skilled in the art, preferably carries out melting mixing in Banbury mixer in the present invention; The temperature of described melting mixing is preferably 80 DEG C��110 DEG C, it is more preferable to be 100 DEG C; The time of described melting mixing is preferably 5��10min, it is more preferable to be 8min.
According to the present invention, those skilled in the art can performance needed for product, such as one or more performances needing carbon dioxide-epoxy propane copolymer porous plastics to have in good aging resistance, processing characteristics and special color, and in raw material, preferably can add corresponding additives for plastics again, then carry out melting mixing. Described additives for plastics be preferably in oxidation inhibitor, lubricant, pigment, weighting agent and bubble stabilizer one or more, its contamination and upper described identical, does not repeat them here.
After completing the melting mixing to carbon dioxide-epoxy propane copolymer, elastomerics, poly-hexanodioic acid/butylene terephthalate and whipping agent, the molten mixture obtained is suppressed, obtains thin slice. The method of described compacting is not had special restriction by the present invention, is drawing method well known to those skilled in the art, and the present invention preferably adopts mill to suppress; The thickness of the thin slice obtained after described compacting is preferably 1��5mm, it is more preferable to be 2��3mm.
After thin slice after being suppressed, carried out moulded from foam, obtained carbon dioxide-epoxy propane copolymer porous plastics. According to the present invention, this step is preferably specially: the thin slice that obtains after compacting is cooled to room temperature, then carries out foaming after mold pressing, pressure release, obtains carbon dioxide-epoxy propane copolymer porous plastics. The restriction that the present invention is not special to the method for described moulded from foam, adopts the method for moulded from foam well known to those skilled in the art, it is preferable that carry out moulded from foam on vulcanizing press; The temperature of described moulded from foam is preferably 180 DEG C��200 DEG C; The pressure of described moulded from foam is preferably 3��15MPa; The time of described moulded from foam is preferably 3��10min.
Experimental result shows, the tensile strength of carbon dioxide-epoxy propane copolymer porous plastics prepared by the present invention is 220��270Kpa, and elongation at break is 9%��13%, and compressive strength is 21��26Kpa.
In order to the present invention is described further, below in conjunction with embodiment, elastomerics provided by the invention and carbon dioxide-epoxy propane copolymer porous plastics are described in detail.
Reagent used in following examples is commercially available: carbon dioxide-epoxy propane copolymer used is bought by Taizhou, Zhejiang Bang Feng plastics company limited and obtained; Poly-hexanodioic acid/butylene terephthalate used is bought by Nantong Hua Sheng novel material company limited and is obtained; Cellmic C 121 used, zinc oxide, calcium carbonate, toner, stearic acid and silicone oil are bought by market and are obtained; The median size of Cellmic C 121 is about 20 ��m.
Embodiment 1
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 1.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 100000g/mol, 5 weight parts, the stearic acid of 0.1 weight part, the 1.1 of 10 weight parts is mixed by 1.2 with the poly-hexanodioic acid/butylene terephthalate of 150 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 190 DEG C, pressure is 10MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
Scanning electronic microscope is utilized to analyze obtaining carbon dioxide-epoxy propane copolymer porous plastics in 1.2, obtain its stereoscan photograph, as shown in Figure 1, the carbon dioxide-epoxy propane copolymer foam cell even structure that as seen from Figure 1 prepared by embodiment 1.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 1.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 1.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 2
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 2.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
2.2 by the zinc oxide of the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 80000g/mol, 2 weight parts, 0.5 weight part, the stearic acid of 0.1 weight part, oxidation inhibitor 626,10 weight part of 0.1 weight part 2.1 in the elastomerics that obtains mix in mixing machine with the poly-hexanodioic acid/butylene terephthalate of 50 weight parts, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 180 DEG C, pressure is 5MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 2.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 2.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 3
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 3.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 180000g/mol, 10 weight parts, the stearic acid of 0.1 weight part, the 3.1 of 20 weight parts is mixed by 3.2 with the poly-hexanodioic acid/butylene terephthalate of 100 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 190 DEG C, pressure is 10MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 3.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 3.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 4
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 4.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the stearic acid of the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 100000g/mol, 15 weight parts, 0.1 weight part, the zinc oxide of 2 weight parts, the 4.1 of 30 weight parts is mixed by 4.2 with the poly-hexanodioic acid/butylene terephthalate of 80 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 180 DEG C, pressure is 10MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 4.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 4.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 5
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 5.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 100000g/mol, 5 weight parts, the stearic acid of 0.1 weight part, the 5.1 of 5 weight parts is mixed by 5.2 with the poly-hexanodioic acid/butylene terephthalate of 200 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 200 DEG C, pressure is 15MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 5.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 5.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 6
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 6.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the carbon black of the stearic acid of the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 100000g/mol, 5 weight parts, 0.1 weight part, 0.001 weight part, the calcium carbonate of 10 weight parts, the 6.1 of 10 weight parts is mixed by 6.2 with the poly-hexanodioic acid/butylene terephthalate of 150 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 190 DEG C, pressure is 10MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 6.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 6.2 is carried out compressive strength test, obtain the results are shown in Table 1.
Embodiment 7
Carbon dioxide-epoxy propane dibasic alcohol and hexa-methylene polymeric polyisocyanate (HDI) are added in reactor according to the feed ratio that hydroxyl and isocyano mol ratio are 1:0.98 by 7.1; 80 DEG C, nitrogen protection when stir carry out reaction 8h obtain prepolymer; prepolymer adds 1; 4-butyleneglycol; 1; 4-butyleneglycol add amount for prepolymer quality 2%, 60 DEG C, nitrogen protection when stir carry out reaction 4h, obtain elastomerics.
The elastomerics obtained in the silicone oil of the Cellmic C 121 of carbon dioxide-epoxy propane copolymer that 100 weight part number-average molecular weights are 100000g/mol, 2 weight parts, 0.1 weight part, the calcium carbonate of 8 weight parts, the 7.1 of 20 weight parts is mixed by 7.2 with the poly-hexanodioic acid/butylene terephthalate of 100 weight parts in mixing machine, then the mixture obtained is added in Banbury mixer, 100 DEG C of melt blending 8min, obtain molten mixture; By mill, the molten mixture obtained is pressed into the thick thin slice of 2mm, it is placed on vulcanizing press after described thin slice is cooled to room temperature to carry out foaming after mold pressing, pressure release, the temperature of described mold pressing is 200 DEG C, pressure is 10MPa, the time be 5min, obtain carbon dioxide-epoxy propane copolymer porous plastics.
According to DINENISO1798-2000 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 7.2 is carried out the test of tensile strength and elongation at break, obtains the results are shown in Table 1.
According to ISO844-2007 standard, the carbon dioxide-epoxy propane copolymer porous plastics obtained in 7.2 is carried out compressive strength test, obtain the results are shown in Table 1.
The performance test results of table 1 carbon dioxide-epoxy propane copolymer porous plastics
The above is only the preferred embodiment of the present invention; it is noted that for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. a carbon dioxide-epoxy propane copolymer porous plastics, it is characterised in that, comprising:
Described elastomerics obtains through alcohol compound chain extension after reacting by poly (propylene carbonate) dibasic alcohol and diisocyanate compound; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol;
Described elastomerics obtains according to following step:
S1) poly (propylene carbonate) dibasic alcohol is mixed with diisocyanate compound, react under protection of inert gas, obtain prepolymer;
S2) described prepolymer is mixed with alcohol compound, react under protection of inert gas, obtain elastomerics; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
2. carbon dioxide-epoxy propane copolymer porous plastics according to claim 1, it is characterised in that, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 80000��200000g/mol.
3. carbon dioxide-epoxy propane copolymer porous plastics according to claim 1, it is characterised in that, the molecular weight distribution of described carbon dioxide-epoxy propane copolymer is 1.5��7.0.
4. carbon dioxide-epoxy propane copolymer porous plastics according to claim 1, it is characterised in that, described whipping agent is sulfohydrazide type blowing agent and/or azo foaming agent.
5. the preparation method of a carbon dioxide-epoxy propane copolymer porous plastics, it is characterised in that, comprise the following steps:
After the whipping agent melting mixing of the poly-hexanodioic acid/butylene terephthalate of the elastomerics of the carbon dioxide-epoxy propane copolymer of 100 weight parts, 5��50 weight parts, 50��200 weight parts and 2��15 weight parts, carry out suppressing, moulded from foam, obtain carbon dioxide-epoxy propane copolymer porous plastics; Described elastomerics obtains through alcohol compound chain extension after reacting by poly (propylene carbonate) dibasic alcohol and diisocyanate compound; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol;
Described elastomerics obtains according to following step:
S1) poly (propylene carbonate) dibasic alcohol is mixed with diisocyanate compound, react under protection of inert gas, obtain prepolymer;
S2) described prepolymer is mixed with alcohol compound, react under protection of inert gas, obtain elastomerics; Described alcohol compound is dibasic alcohol and/or polyvalent alcohol.
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| WO2010028362A1 (en) * | 2008-09-08 | 2010-03-11 | Novomer, Inc. | Polycarbonate polyol compositions and methods |
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| WO2010028362A1 (en) * | 2008-09-08 | 2010-03-11 | Novomer, Inc. | Polycarbonate polyol compositions and methods |
| CN103030766A (en) * | 2013-01-04 | 2013-04-10 | 中国科学院长春应用化学研究所 | Carbon dioxide-based poly (carbonic ester-ether) polyurethane and preparation method thereof |
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