CN1116330C - Modified polyurethane elastomer material and its preparing method and use - Google Patents
Modified polyurethane elastomer material and its preparing method and use Download PDFInfo
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- CN1116330C CN1116330C CN 00114428 CN00114428A CN1116330C CN 1116330 C CN1116330 C CN 1116330C CN 00114428 CN00114428 CN 00114428 CN 00114428 A CN00114428 A CN 00114428A CN 1116330 C CN1116330 C CN 1116330C
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Abstract
The present invention discloses a modified polyurethane elastomeric material, a preparation method thereof and the purpose. The material is a novel polyurethane film material which is obtained by that nitration lignin, castor oil type polyurethane, chain extender 1, and 1, 4-butanediol are dissolved in tetrahydrofuran, are mixed, and are solidified under the proper condition; compared with the castor oil polyurethane membrane which is not modified, the tensile strength and the breaking extension rate are obviously improved. The material has the elastic characteristic similar to rubber, can fully recover deformation, and can make biodegradation; the present invention has the advantages of simple and convenient production process, can be used for biodegradable paint or film materials, is suitable for the field of medicine, daily service, chemical industry, environmental protection, etc.
Description
The present invention relates to a kind of modified polyurethane elastomer material and its production and use, specifically a kind of castor oil type polyurethane elastomer material that contains a small amount of nitration of lignin and its production and use, belong to filed of functional, also belong to the natural polymer field.
Xylogen is used as fuel mostly as the byproduct of paper industry, but it is considered to have the potentiality that become chemical industry basic raw material and preparation Biodegradable material with nontoxic, low-cost and biodegradable characteristics.Up to now, utilize xylogen to prepare plastics (United States Patent (USP), 4131573,1978), resin (Canadian Patent, 654728,1962) and tackiness agent (United States Patent (USP), 3931072,1976; Material and as research (United States Patent (USP), 2610954,1962 of rubber accelerator such as 3886101,1974); German Patent, 1165844,1964) remarkable progress (Progress in Polymer Science, 17,611,1992 have been obtained; The polymer circular, 4,240,1992).But these researchs are mostly at sulfonated lignin and kraft paper xylogen, and the applied research of byproduct-alkali lignin that the southern alkaline process of China is obtained does not appear in the newspapers as yet.Interpenetrating polymer networks is a powerful measure of improving material property in the polymeric material field.Resins, epoxy-castor oil type polyurethane grafting interpenetrating polymer networks material is with the increase of epoxy resin content, and the tensile strength of its material increases but elongation at break reduces (Journal of Applied Polymer Science, 70,1649,1998); Polystyrene-Viscotrol C urethane interpenetrating polymer networks material shows the plasticity (Polymer Engineering and Science, 18,200,1978) of polystyrene gradually with the increase of polystyrene content.
The purpose of this invention is to provide a kind of polyurethane elastomer material of modification-contain castor oil type polyurethane elastomer material of nitration of lignin and its production and use, mechanical properties such as the tensile strength of this modified polyurethane elastomer material, elongation at break should be than being significantly improved before the modification, and can be used as biodegradable preventing water coating and mould material.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of modified polyurethane elastomer material, it be with isocyanato (NCO) and hydroxyl (molar ratio OH) is 2.0 castor oil type polyurethane prepolymer, 1,4-butyleneglycol and nitrogen content 6.32%, weight-average molecular weight 0.5～2.0 * 10
4Nitration of lignin be dissolved in respectively in the tetrahydrofuran solvent, mix then, solidified 6～8 hours down and obtain at 15-40 ℃ respectively, the massfraction of the nitration of lignin wherein ratio of material total mass (nitration of lignin with) is 1～6%.
A kind of method for preparing the polyurethane elastomer material of above-mentioned modification: with tetrahydrofuran (THF) do solvent be made into respectively massfraction be 28.6% isocyanato (NCO) and hydroxyl (molar ratio OH) be 2.0 castor oil type polyurethane prepolymer, 18.4% 1, the solution of 4-butyleneglycol and 1.0～5.9% nitration of lignin, mix by 1: 1: 1 volume ratio then, curing made the polyurethane film that contains nitration of lignin (massfraction is 1～6%) in 6～8 hours under 15-40 ℃ respectively, promptly contained the castor oil type polyurethane elastomer material of nitration of lignin.
According to technical scheme of the present invention, the preparation method of described nitration of lignin is: after 20 gram bamboo wood alkali lignins (byproduct of paper industry) and the mixing of 35mL nitrosonitric acid, drip the 22mL diacetyl oxide, in cryosel stirred in water bath 12～18 hours, the solid sediment that reaction is obtained was repeatedly with the frozen water washing and surpass centrifugal settling and obtain neutral, nitrogen content 6.32%, weight-average molecular weight 0.5～2.0 * 10 then
4Nitration of lignin; It has good solubility in ethyl acetate and tetrahydrofuran (THF).
According to technical scheme of the present invention, the preparation of castor oil type polyurethane prepolymer is with reference to the method (Macromolecules, 12,360,1979) of L.H.Sperling.Viscotrol C dehydration one hour under 100 ℃, the pressure of 20mmHg is heavily steamed before tolylene diisocyanate uses.Viscotrol C is added dropwise to tolylene diisocyanate lentamente 40 ℃ of following stirring reactions 2 hours.The mass ratio of Viscotrol C and tolylene diisocyanate is 57: 29, the conversion obtain isocyanato (NCO) and hydroxyl (molar ratio OH) is 2.0.
Modified polyurethane elastomer material of the present invention has excellent mechanical property, and biodegradable.Therefore, this material can be used as super quality and competitive price, biodegradable, pollution-free green coating and mould material, also can be used as new resilient material and is used for fields such as medicine, daily, chemical industry and environmental protection.
Modified polyurethane elastomer material of the present invention is to have introduced a small amount of nitration of lignin when synthetic preparation, make the material after the modification all increase nearly one times by graft crosslinking reaction, show that nitration of lignin is very effective to the enhancing and the toughening effect of polyurethane material than mechanical properties such as the tensile strength of original castor oil type polyurethane and elongation at breaks; Graft reaction has taken place between nitration of lignin and castor oil type polyurethane in the testimonial material in infrared spectra, transmission electron microscope etc. as a result, simultaneously the stronger hydrogen bond of intermolecular existence and thermostability is improved.Material presents good consistency and two kinds of intermolecular networks obviously increase, and causes intensity and elastic raising thus.The material that obtains has the elasticity of rubber like, and its tensile deformation can recover fully.This material also has biodegradable in addition, can be used as water-repellancy green coating component or biodegradable functional film material and is used for the green chemical industry field.The byproduct that the present invention utilizes this inexpensive, abundant, biodegradable paper industry of alkali lignin is as one of raw material of preparation modified polyurethane elastomer material, both reach the purpose that increases mechanical properties such as tensile strength of material and elongation at break simultaneously, improved the economic value added that alkali lignin uses again.That therefore should invent is high in technological content, has the characteristics of easy exploiting utilization and changing waste into valuables.
The present invention is a nitrating agent with nitrosonitric acid and diacetyl oxide, makes nitration of lignin with the reaction of bamboo wood alkali lignin, and makes castor oil type polyurethane coating or the mould material that contains nitration of lignin first.A small amount of nitration of lignin has very strong reactive behavior, and it and castor oil type polyurethane reaction form the intermolecular cross-linking network, thereby its intensity and elasticity are improved greatly.What should particularly point out is that tensile strength of material and the elongation at break that obtains increased nearly one times simultaneously, and presents the stress-strain feature of rubber.Therefore this invention has significant technical progress.
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
20 gram bamboo wood alkali lignins and 35mL nitrosonitric acid are mixed back dropping 22.5mL diacetyl oxide, constantly stirred 18 hours in the cryosel water-bath, the solid sediment that reaction is obtained washs and surpasses centrifugal settling with frozen water repeatedly and obtains neutral, nitrogen content 6.32%, weight-average molecular weight 1.1 * 10 then
4Nitration of lignin; It has good solubility in ethyl acetate and tetrahydrofuran (THF).
Viscotrol C dehydration one hour under 100 ℃, the pressure of 20mmHg is heavily steamed before tolylene diisocyanate uses.Viscotrol C is added dropwise to tolylene diisocyanate lentamente 40 ℃ of following stirring reactions 2 hours.The mass ratio of Viscotrol C and tolylene diisocyanate is 57: 29, the conversion obtain isocyanato (NCO) and hydroxyl (molar ratio OH) is 2.0.
With tetrahydrofuran (THF) do solvent be made into respectively massfraction be 28.6% castor oil type polyurethane prepolymer, 18.4% 1, the solution of 4-butyleneglycol and 1.4% nitration of lignin, mix by 1: 1: 1 volume ratio then, on the tetrafluoroethylene plate, make the polyurethane film that contains nitration of lignin (massfraction is 1.4%) by the hydrostomia method, solidification value is 20 ± 2 ℃, 8 hours set times.The film that the mechanical property of this film obtains than comparative example 1 has increased nearly one times.
Embodiment 2
The preparation method of polyurethane film who contains nitration of lignin (massfraction is 2.9%) is with embodiment 1, and the massfraction that only adds nitration of lignin-tetrahydrofuran solution is 2.8%.The tensile strength of this film and elongation at break all increase than the material that embodiment 1 obtains.
Embodiment 3
Reduce at the suitable but elongation at break of 35 ± 2 ℃ of tensile strengths of solidifying the polyurethane film that obtained in 6 hours down and film that embodiment 1 obtains according to embodiment 1 proportioning raw materials and method, compare mechanical property with comparative example 2 and be significantly improved.
Embodiment 4
Solidify the polyurethane film that obtained in 6 hours according to embodiment 2 proportioning raw materials and method down at 35 ± 2 ℃.Compare with the film that embodiment 2 obtains, the tensile strength of this film quite and elongation at break increase; Compare with the film that embodiment 3 obtains, the tensile strength and the elongation at break of this film all are significantly improved.Particularly the film that obtains than comparative example 1 and 2 of its elongation at break has increased more than one times.
Embodiment 5
The preparation method of polyurethane film who contains nitration of lignin (massfraction is 5.5%) is with embodiment 1, the massfraction that only adds nitration of lignin-tetrahydrofuran solution be 5.4% and solidification value be 35 ± 2 ℃, 6 hours set times.The film that this tensile strength of material and embodiment 3 obtain is suitable, but elongation at break increases.Comparative example 1
Method by embodiment 1 makes the castor oil type polyurethane prepolymer.Making solvent with tetrahydrofuran (THF), to be made into massfraction respectively be 1 of 28.6% castor oil type polyurethane prepolymer and 18.4%, the 4-butyleneglycol, mix by 1: 1 volume ratio then, on the tetrafluoroethylene plate, make the castor oil type polyurethane film by the hydrostomia method, solidification value is 20 ± 2 ℃, 8 hours set times.Comparative example 2
Method with comparative example 1 makes the castor oil type polyurethane film, but solidification value is 35 ± 2 ℃, 6 hours set times.
The mechanical property of subordinate list 1 nitration of lignin-castor oil type polyurethane film
The feature mechanical property
Nitration of lignin content temperature of reaction σ
b/ MPa ε
b/ %
10 20 ± 2 ℃ 11.73 126 of comparative example
1 1.4% 20 ± 2 ℃ 20.80 211 of embodiment
2 2.9% 20 ± 2 ℃ 22.85 239 of embodiment
20 35 ± 2 ℃ 14.15 106 of comparative example
3 1.4% 35 ± 2 ℃ 20.07 164 of embodiment
4 2.9% 35 ± 2 ℃ 22.90 258 of embodiment
Embodiment annotates for 5 5.5% 35 ± 2 ℃ 19.88 215: Mechanics Performance Testing records on the CMT6503 instrument of Shenzhen SANS testing tool company with reference to State Standard of the People's Republic of China GB4456-84, and draw speed is 100mm/min.
Claims (5)
1, a kind of modified polyurethane elastomer material, it is characterized in that: it is that molar ratio by isocyanato and hydroxyl is 2.0 castor oil type polyurethane prepolymer, 1,4-butyleneglycol and nitration of lignin are dissolved in the tetrahydrofuran solvent respectively, mix then, solidify 6～8 hours gained down at 15-40 ℃, wherein the massfraction of nitration of lignin is 1～6%, the preparation method of described castor oil type polyurethane prepolymer is as follows: Viscotrol C is added dropwise to tolylene diisocyanate lentamente 40 ℃ of following stirring reactions 2 hours, and the mass ratio of different two cyanates of Viscotrol C and toluene is 57: 29.
2, a kind of method for preparing the described modification polyurethane elastomer material of claim 1, it is characterized in that: with tetrahydrofuran (THF) do solvent be made into respectively massfraction be the molar ratio of 28.6% isocyanato and hydroxyl be 2.0 castor oil type polyurethane prepolymer, 18.4% 1, the solution of the nitration of lignin of 4-butyleneglycol and 1.0-5.9%, mix by 1: 1: 1 volume ratio then, solidify the product that obtained in 6～8 hours down at 15-40 ℃ respectively and be the castor oil type polyurethane resilient material that contains nitration of lignin.
3, method according to claim 2 is characterized in that: the nitrogen content of described nitration of lignin is 6.32%, weight-average molecular weight is 0.5～2.0 * 10
4
4, method according to claim 3, it is characterized in that described nitration of lignin prepares gained by following method: after 20 gram bamboo wood alkali lignins and the mixing of 35mL nitrosonitric acid, drip the 22mL diacetyl oxide, in cryosel stirred in water bath 12～18 hours, the solid sediment that reaction is obtained was repeatedly with the frozen water washing and surpass centrifugal settling and obtain nitration of lignin then.
5, the poly-propylhomoserin elastomer material of the described modification of claim 1 is as biodegradable coating or mould material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00114428 CN1116330C (en) | 2000-03-16 | 2000-03-16 | Modified polyurethane elastomer material and its preparing method and use |
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| CN 00114428 CN1116330C (en) | 2000-03-16 | 2000-03-16 | Modified polyurethane elastomer material and its preparing method and use |
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| CN1314426A CN1314426A (en) | 2001-09-26 |
| CN1116330C true CN1116330C (en) | 2003-07-30 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2450852A1 (en) * | 2001-06-15 | 2002-12-27 | National Institute Of Advanced Industrial Science And Technology | Lignin-containing polyurethane and process for producing the same |
| CN1302072C (en) * | 2005-10-12 | 2007-02-28 | 太原理工大学 | Modified polyurethane composition and preparation thereof |
| CN102260366B (en) * | 2010-05-29 | 2014-04-02 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
| EP3115544B1 (en) * | 2014-03-07 | 2020-10-14 | Kureha Corporation | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| CN109485824A (en) * | 2018-10-12 | 2019-03-19 | 华南理工大学 | A kind of thermosetting property lignin-base polyurethane elastomer of recyclable processing and preparation method thereof |
| CN113103560B (en) * | 2021-04-14 | 2022-05-13 | 中国科学技术大学 | High-strength polyurethane material and preparation method thereof |
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