CN102977330A - Preparation method for degradable polyurethane materials - Google Patents
Preparation method for degradable polyurethane materials Download PDFInfo
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- CN102977330A CN102977330A CN2012104577466A CN201210457746A CN102977330A CN 102977330 A CN102977330 A CN 102977330A CN 2012104577466 A CN2012104577466 A CN 2012104577466A CN 201210457746 A CN201210457746 A CN 201210457746A CN 102977330 A CN102977330 A CN 102977330A
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Abstract
The invention discloses a preparation method for degradable polyurethane materials, and belongs to the field of chemical engineering and high polymer chemistry. Mixture of liquefaction produced materials and starch is used as polyhydric alcohols and undergoes a polymerization reaction along with polyisocyanates under the existing of catalytic agent, surface active agent and foaming agent. The degradable polyurethane materials are obtained after injection molding and ripening of the mixture. Through adjustment of technological parameters, polyurethane products of foaming type, soft type, semi-hard type and hard type can be obtained. Relative to full-starch materials, the products have the advantages of being good in mechanical strength and water resistance performance. Relative to fully liquefied high polymer materials, the products have the advantage of being low in cost. A soil test shows that the products have good biological degradability and can be degraded within two years. The implementation of the preparation method not only can supply a high and new technology for treating white pollution and protecting environment, but also is beneficial for enlarging high-efficiency use of natural polymer such as straws and the starch, and economy development of countryside can be stimulated.
Description
Technical field
The invention belongs to chemical engineering and chemical field, particularly a kind of degradable polyurethane material preparation method.
Background technology
Polyurethane material has been widely used in nearly all industries such as aviation, automobile, building, furniture and packing with its unique excellent properties.Polyurethane synthetic material has become one of material with the fastest developing speed in recent decades.Yet traditional polyurethane material is difficult to degraded, has brought serious problems such as " white pollutions " after discarding; On the other hand, the main raw material of polyurethane material derives from petrochemical complex, and the fossil energies such as oil are Nonrenewable energy resources, peter out.Therefore, it is extremely urgent to seek new plastic raw materials and development environment close friend's degradation material.Starch has that output is large, price is low, degradable, renewable and reactive behavior be than advantages of higher, is the natural polymer that is used to the earliest develop degradation material.But there are the problems such as mechanical property and poor water resistance in starch-based material, has seriously limited Application Areas and the scope of full starch plastic.In recent years, take agricultural crop straw as raw material, be translated into the liquid substance that contains great amount of hydroxy group, very high reactive behavior is arranged by certain technology, become the focus of research, and liquefying biomass can replace traditional polyethers or polyester polyol to produce the macromolecular materials such as degradable polyurethane, becomes whole world research worker's common recognition.But, because the biomass liquefying cost is higher at present, limited the application of liquefying biomass in field of polymer technology.
Summary of the invention
The purpose of this invention is to provide a kind of degradable polyurethane material preparation method, it is characterized in that, utilize the blend of liquefying biomass and starch to prepare the degradable polyurethane material for raw material; Namely take the blend of liquefying biomass and starch as polyvalent alcohol, in the presence of catalyzer, tensio-active agent and whipping agent, with the polyisocyanic acid polyisocyanate polyaddition, adjust the ratio of quality and the number of copies of raw material, can obtain foaming kind, soft class, semi-rigid class and hard class polyurethane product; Preparation degradable polyurethane material; Comprise the steps:
1) according to ratio of quality and the number of copies, prepare raw material, mainly comprise:
2) according to aforementioned proportion liquefying biomass and starch blend, catalyzer, tensio-active agent and whipping agent are fully mixed; 3) in step 2) mixture in to add the isocyano index be the polyisocyanates of 0.4-1.5, and high-speed stirring until milky white phenomenon occur;
4) casting obtains polyurethane product by the mixture that step 3) obtains after polymerization, the slaking.
Described polyisocyanates is that polyisocyanates is tolylene diisocyanate (TDI) or diphenylmethanediisocyanate (MDI) or poly methylene poly phenyl poly isocyanate (PAPI).
Described liquefying biomass is to be obtained by Thermochemical Liquefaction method commonly used, namely take NSC 11801 as liquefying agent, the vitriol oil is catalyzer, 60-80 min liquefies biomass material under 150 ℃-180 ℃; Its biomass material comprises various agricultural crop straws, wood powder or bamboo powder.
Described starch is ative starch or treated starch, and wherein treated starch is a kind of and two or more in Acid modified starch, oxidation modification starch and the cross-linking starch.Acid modified starch comprises maizenic acid treated starch, wheat Acid modified starch and potato Acid modified starch etc.; Sumstar 190 comprises cassava oxidized starch, maize oxidized starch, wheat Sumstar 190, potato oxidized starch etc.; Cross-linking starch comprises etherificate cross-linking starch and esterified crosslinked starch etc.
Described catalyzer comprises triethylamine, N, N-dimethyl hexadecylamine, diethyl triamine, dimethyl benzylamine, triethylenediamine, N-methylmorpholine, N-Ethylmorphine quinoline, trolamine, diethanolamine, thanomin, pyridine, lutidine etc. for the mixture tertiary amine catalyst for tertiary amine catalyst or organo-metallic catalyst or tertiary amine catalyst and organo-metallic catalyst.Organo-metallic catalyst comprises dibutyltin dilaurate, stannous octoate etc.
Described tensio-active agent is silicone oil.
Described whipping agent is water or chloro-fluoro-carbon kind whipping agent, Hydrochlorofluorocarbons class whipping agent, pentamethylene, methylene dichloride or liquid carbon dioxide.Wherein the chloro-fluoro-carbon kind whipping agent comprises fluoro trichloromethane, methyl chlorofluoride etc.; Hydrochlorofluorocarbons class whipping agent comprises a fluorine ethylene dichloride, trifluorobichloroethane, difluorochloromethane, fluoro trichloromethane.
Beneficial effect of the present invention mainly is to utilize the blend of liquefying biomass and starch to prepare the degradable polyurethane material for raw material, with the advantage of giving full play to liquefying biomass and starch, the obvious efficient utilization that enlarges the biomass that comprise stalk, promote rural economic development; To solve present starch plastics mechanical property and poor water resistance and the high shortcoming of liquefying biomass based high molecular material price.Have following advantage:
1. the quality of goods is high.Take polyurethane film as example, tensile strength is higher by 50% than full starch film, and elongation at break is high by 100%, and water tolerance is better;
2. its goods price is low, compares with full liquefying biomass polyurethane material, and price is the highest can be reduced more than 150%, can greatly promote liquefying biomass in the application in the macromolecular material fields such as urethane;
3. its goods can be degradable in 2 years in soil after discarding, and for administering " white pollution ", protection of the environment, provides new and high technology;
Embodiment
The invention provides a kind of degradable polyurethane material preparation method, utilize the blend of liquefying biomass and starch to prepare the degradable polyurethane material for raw material; Namely take the blend of liquefying biomass and starch as polyvalent alcohol, in the presence of catalyzer, tensio-active agent and whipping agent, with the polyisocyanic acid polyisocyanate polyaddition, adjust the ratio of quality and the number of copies of raw material, can obtain foaming kind, soft class, semi-rigid class and hard class polyurethane product; The below further specifies characteristics of the present invention with example.
Embodiment 1
Take NSC 11801 as liquefying agent, the vitriol oil is catalyzer, 60min liquefies maize straw under 160 ℃, getting liquefaction maize straw 60g, maizenic acid treated starch 40g, triethylamine 0.25g, dibutyl tin laurate 0.25g, silicone oil 1.0g, water 0.5g fully mixes, then adding poly methylene poly phenyl poly isocyanate 40g(isocyano index is 0.6), fully mix again until after the appearance of milky white phenomenon, be injected in the mould, take out after the slaking, measure its performance.
Test result is: the tensile strength of polyurethane foam is 2.0MPa; Elongation at break is 95%; Have excellent water-resistance; The soil degrading test shows that degraded in 2 months degraded in 25%, 6 month surpasses 50%.
Embodiment 2
Take NSC 11801 as liquefying agent, the vitriol oil is catalyzer, 70min liquefies wood powder under 170 ℃, get liquefaction wood powder 50g, cassava oxidation modification starch 50g, triethylamine 0.25g, dibutyl tin laurate 0.25g, silicone oil 1.0g, water 0.5g fully mix, then adding poly methylene poly phenyl poly isocyanate 40g(isocyano index is 0.75), fully mix again until after the appearance of milky white phenomenon, be injected in the mould, take out after the slaking, measure its performance.
Test result is: the tensile strength of polyurethane material is 2.6MPa; Elongation at break is 125%; Have excellent water-resistance; The soil degrading test shows that degraded in 2 months degraded in 30%, 6 month surpasses 55%.
Claims (10)
1. a degradable polyurethane material preparation method is characterized in that, utilizes the blend of liquefying biomass and starch to prepare the degradable polyurethane material for raw material; Namely take the blend of liquefying biomass and starch as polyvalent alcohol, in the presence of catalyzer, tensio-active agent and whipping agent, with the polyisocyanic acid polyisocyanate polyaddition, adjust the ratio of quality and the number of copies of raw material, can obtain foaming kind, soft class, semi-rigid class and hard class polyurethane product; Preparation degradable polyurethane material; Comprise the steps:
1) according to ratio of quality and the number of copies, it is as follows to prepare raw material:
2) according to aforementioned proportion liquefying biomass and starch blend, catalyzer, tensio-active agent and whipping agent are fully mixed;
3) in step 2) mixture in to add the isocyano index be the polyisocyanates of 0.4-1.5, and high-speed stirring until milky white phenomenon occur;
4) casting obtains polyurethane product by the mixture that step 3) obtains after polymerization, the slaking.
2. described degradable polyurethane material preparation method according to claim 1 is characterized in that described polyisocyanates is tolylene diisocyanate or diphenylmethanediisocyanate or poly methylene poly phenyl poly isocyanate.
3. described degradable polyurethane material preparation method according to claim 1, it is characterized in that, described liquefying biomass is to be obtained by Thermochemical Liquefaction method commonly used, namely take NSC 11801 as liquefying agent, the vitriol oil is catalyzer, 60-80 min liquefies biomass material under 150 ℃-180 ℃; Its biomass material is one or more the compound in various agricultural crop straws, wood powder and the bamboo powder.
4. described degradable polyurethane material preparation method according to claim 1 is characterized in that described starch is ative starch or treated starch; Wherein treated starch be in Acid modified starch, oxidation modification starch and the cross-linking starch one or more, Acid modified starch comprises maizenic acid treated starch, wheat Acid modified starch and potato Acid modified starch; Sumstar 190 comprises cassava oxidized starch, maize oxidized starch, wheat Sumstar 190 and potato oxidized starch; Cross-linking starch comprises etherificate cross-linking starch and esterified crosslinked starch.
5. described degradable polyurethane material preparation method according to claim 1 is characterized in that described catalyzer is tertiary amine catalyst or organo-metallic catalyst, or the mixture of tertiary amine catalyst and organo-metallic catalyst.
6. described degradable polyurethane material preparation method according to claim 5, it is characterized in that, described tertiary amine catalyst comprises triethylamine, N, in N-dimethyl hexadecylamine, diethyl triamine, dimethyl benzylamine, triethylenediamine, N-methylmorpholine, N-Ethylmorphine quinoline, trolamine, diethanolamine, thanomin, pyridine and the lutidine more than one.
7. described degradable polyurethane material preparation method according to claim 5 is characterized in that, described organo-metallic catalyst be in dibutyltin dilaurate and the stannous octoate more than one.
8. described degradable polyurethane material preparation method according to claim 1 is characterized in that described tensio-active agent is silicone oil.
9. described degradable polyurethane material preparation method according to claim 1 is characterized in that described whipping agent is water, chloro-fluoro-carbon kind whipping agent, Hydrochlorofluorocarbons class whipping agent, pentamethylene, methylene dichloride or liquid carbon dioxide.
10. described degradable polyurethane material preparation method according to claim 9 is characterized in that described chloro-fluoro-carbon kind whipping agent is fluoro trichloromethane or methyl chlorofluoride; Described Hydrochlorofluorocarbons class whipping agent is a fluorine ethylene dichloride, trifluorobichloroethane, difluorochloromethane or fluoro trichloromethane.
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| CN2012104577466A CN102977330A (en) | 2012-11-14 | 2012-11-14 | Preparation method for degradable polyurethane materials |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356346A (en) * | 2014-10-22 | 2015-02-18 | 内蒙古农业大学 | Foaming material, preparation method and application |
| CN108499534A (en) * | 2018-03-30 | 2018-09-07 | 南宁学院 | A kind of graphene-containing metal organic framework dense gas separation hybrid material and preparation method |
| CN110423483A (en) * | 2019-08-14 | 2019-11-08 | 淮北市菲美得环保科技有限公司 | A kind of biology base degradable foam materials and preparation method thereof |
| CN111019331A (en) * | 2019-12-24 | 2020-04-17 | 齐鲁工业大学 | Polyester elastomer film and preparation method thereof |
| CN111479838A (en) * | 2017-12-18 | 2020-07-31 | 科思创德国股份有限公司 | Flame-retardant rigid polyurethane foam |
| CN111763302A (en) * | 2020-07-08 | 2020-10-13 | 清远新力化机有限公司 | TPU (thermoplastic polyurethane) formula for thin film and preparation method thereof |
| CN113999361A (en) * | 2021-11-24 | 2022-02-01 | 浙江高裕家居科技股份有限公司 | Plant-based polyurethane material and preparation method thereof |
| CN115322123A (en) * | 2022-08-15 | 2022-11-11 | 万华化学集团股份有限公司 | Halogen modified azo diamine chain extender, preparation method and application thereof |
| CN115417964A (en) * | 2022-09-21 | 2022-12-02 | 台州益普高分子材料有限公司 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356346A (en) * | 2014-10-22 | 2015-02-18 | 内蒙古农业大学 | Foaming material, preparation method and application |
| CN111479838A (en) * | 2017-12-18 | 2020-07-31 | 科思创德国股份有限公司 | Flame-retardant rigid polyurethane foam |
| CN108499534B (en) * | 2018-03-30 | 2021-03-16 | 南宁学院 | Compact gas separation hybrid material containing graphene metal organic framework and preparation method thereof |
| CN108499534A (en) * | 2018-03-30 | 2018-09-07 | 南宁学院 | A kind of graphene-containing metal organic framework dense gas separation hybrid material and preparation method |
| CN110423483A (en) * | 2019-08-14 | 2019-11-08 | 淮北市菲美得环保科技有限公司 | A kind of biology base degradable foam materials and preparation method thereof |
| CN111019331A (en) * | 2019-12-24 | 2020-04-17 | 齐鲁工业大学 | Polyester elastomer film and preparation method thereof |
| CN111019331B (en) * | 2019-12-24 | 2021-11-02 | 齐鲁工业大学 | Polyester elastomer film and preparation method thereof |
| CN111763302A (en) * | 2020-07-08 | 2020-10-13 | 清远新力化机有限公司 | TPU (thermoplastic polyurethane) formula for thin film and preparation method thereof |
| CN113999361A (en) * | 2021-11-24 | 2022-02-01 | 浙江高裕家居科技股份有限公司 | Plant-based polyurethane material and preparation method thereof |
| CN115322123A (en) * | 2022-08-15 | 2022-11-11 | 万华化学集团股份有限公司 | Halogen modified azo diamine chain extender, preparation method and application thereof |
| CN115322123B (en) * | 2022-08-15 | 2024-02-02 | 万华化学集团股份有限公司 | Halogen modified azo diamine chain extender, preparation method and application thereof |
| CN115417964A (en) * | 2022-09-21 | 2022-12-02 | 台州益普高分子材料有限公司 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
| CN115417964B (en) * | 2022-09-21 | 2024-02-23 | 台州益普高分子材料有限公司 | Degradable polyurethane, preparation method thereof and garden water pipe prepared from degradable polyurethane |
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Application publication date: 20130320 |