CN101250329A - Crop straw-polyurethane foam composite material and method for preparing same - Google Patents
Crop straw-polyurethane foam composite material and method for preparing same Download PDFInfo
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- CN101250329A CN101250329A CNA2008100642845A CN200810064284A CN101250329A CN 101250329 A CN101250329 A CN 101250329A CN A2008100642845 A CNA2008100642845 A CN A2008100642845A CN 200810064284 A CN200810064284 A CN 200810064284A CN 101250329 A CN101250329 A CN 101250329A
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Abstract
Crop straw-polyurethane foam composite material and a preparation process thereof relate to foam composite material and the preparation process. The invention solves the problems existing in the current polyurethane foam of lacking resource and low straw utilization. The invention is mainly prepared by crop straw, polyisocyanate or isocyanate prepolymer, water, foam kicker, foam stabilizer and foaming agent. The preparation process of the invention comprises abutting and sealing mould which is used to place crushed straw aggregates with a foaming box which is added with the mixture which is prepared by agitating polyisocyanate or isocyanate prepolymer, water, foam kicker, foam stabilizer and foaming agent, conducting foaming reaction for 1-30min, filling all gaps in crushed aggregates of crop straw with polyurethane foam by means of foaming expansion force, adhering crushed aggregates together, and placing for 1-24h under constant temperature. The invention makes the crop straw be fully used. The composite material has excellent buffering capacity, strength, heat insulation and sensitivity to notching, and can protect environment.
Description
Technical field
The present invention relates to a kind of foamed composite and preparation method thereof.
Background technology
Foam is a kind of indispensable material in people's productive life, relates to the every aspect of people's productive life and scientific technological advance.Yet the production of synthesising foam material depends on limited, the non-renewable petroleum resources of reserves, and along with the consumption day by day of petroleum resources, synthesized polymer material will engender crisis of resource.For this reason, for the mankind's Sustainable development, the petroleum resources situation forces people constantly to seek and uses new, reproducible equivalent material.
Crop material has characteristics such as abundant, the renewable and biological degradation of output, environmental friendliness as the important biomass-based material of a class, be following substitute or part to substitute with petroleum resources be the valuable source of raw-material synthesized polymer material.The crop material annual production of China just surpasses 4,000,000,000 tons, yet abundant crop material resource does not obtain fully and effectively utilizing.Except that the raw material of small part crop material as purposes such as animal-feed, compost, handicraft, most of crop materials or crop material component all are dropped or burn, and cause a large amount of vegetable fibre resources to waste.In recent years, people receive much attention to utilizing the crop material resource to develop biomass industries such as biological material, biomass energy for raw material.
Summary of the invention
The objective of the invention is provides a kind of crop straw-polyurethane foam composite material and preparation method thereof for the shortage of resources that solves existing preparation polyurethane foam, the problem that the straw utilization rate is low.
Crop straw-polyurethane foam composite material of the present invention is mainly made by 50～100 parts of crop materials, 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight.
Crop straw-polyurethane foam composite material of the present invention also comprises 0.01～14.5 part of polyether glycol by weight, and polyether glycol is polyoxyethylene enediol, polyoxyethylene triol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.
Crop material of the present invention is rice straw, wheat straw, corn stalk, sorghum stalk, soybean stalk, mung bean stalk, broad bean stalk, pea stalk, sweet potato vine, potato vine, Ipomoea batatas rattan, peanut stalk, rape stalk, sesame stalk, flax stalk, a kind of or wherein several combination in bluish dogbane stalk, jute stalk, hemp stalk, flax stalk, cotton stalk, sugarcane stem, tobacco stalk and the melon and fruit stalk; Described polyisocyanates is poly methylene poly phenyl poly isocyanate, tolylene diisocyanate, ditan-4,4-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate and 4, a kind of or wherein several combination in the 4-dicyclohexyl methane diisocyanate; Described isocyanic ester performed polymer is that the mol ratio by ester group and hydroxyl is that 1.1～15: 1 polyvalent alcohol and polyisocyanate mixtures obtain at 30～90 ℃ of reaction 0.5～3h, and wherein polyvalent alcohol is polyether glycol or polyester polyol; Described kicker is triethylene diamine, two-(dimethylaminoethyl) ether, trolamine, dimethylethanolamine, N-methylmorpholine, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, N, a kind of or wherein several combination in N-lupetazin, pentamethyl-triethylene diamine, N,N-Dibenzylamine, Tetramethyl Ethylene Diamine, stannous octoate and the dibutyltin dilaurate; Described suds-stabilizing agent is silicone oil or modified silicon oil; Described whipping agent is methylene dichloride, trichloromethane, acetone or pentane.
The preparation method of crop straw-polyurethane foam composite material of the present invention is as follows: one, be that crop material particle below the 30mm is placed in the forming mould of shaper with 50～100 weight part length, make the volume compression of particle reduce 1%～20%, the volume after the fixing compression; Two, under the room temperature in the foam box of shaper, add 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight and stir and make mixture; Three, the forming mould of crushed straw aggregate and the foam box Butt sealing in the step 2 will be held in the step 1, and the gauze of adjusting forming mould bottom just contacts the top of mixture in the foam box, behind foamable reaction 1～30min, at room temperature place ageing 1～24h, in forming mould, promptly get crop straw-polyurethane foam composite material, wherein added 0.01～14.5 part of polyether glycol in the step 2 in the foam box of shaper by weight, polyether glycol is the polyoxyethylene enediol, the polyoxyethylene triol, polyoxypropyleneglycol, the polyoxytrimethylene triol, polytetrahydrofuran diol, the polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.Wherein making mixture by water, kicker, suds-stabilizing agent, whipping agent and polyisocyanates or the stirring of isocyanic ester performed polymer in the step 2 is exactly polyurathamc, and its final reaction product is a polyurethane foam; Polyurathamc foam in the step 3 in the foam box makes in the continuous forming mould that enters shaper that expands of polyurethane foam, fills all spaces in the crop material particle, and crushed straw aggregate is sticked together by means of the foaming and intumescing power of self.
Crop straw-polyurethane foam composite material of the present invention and manufacture method thereof, the contemporary oil that replaces that crop material is utilized fully prepares the polymer foam.This vegetable fibre content of 50%～90% crop material is abundant, biodegradable material because contain for the crop straw-polyurethane foam composite material of the present invention's preparation; but thereby have good resiliency, elasticity, intensity, thermal insulation and a cutting; and can protect environment; therefore can substitute synthetic macromolecule foam materialss such as polyurethane foam, polystyrene foam; as wrapping material, buffer pad material, acoustic panel, construction material and lagging material, Application Areas is very extensive.
Embodiment
Embodiment one: crop straw-polyurethane foam composite material of the present invention is mainly made by 50～100 parts of crop materials, 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight.
Embodiment two: what present embodiment and embodiment one were different is that crop straw-polyurethane foam composite material also comprises 0.01～14.5 part of polyether glycol by weight, and polyether glycol is polyoxyethylene enediol, polyoxyethylene triol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that described crop material is rice straw, wheat straw, corn stalk, sorghum stalk, soybean stalk, mung bean stalk, broad bean stalk, pea stalk, sweet potato vine, potato vine, Ipomoea batatas rattan, peanut stalk, rape stalk, sesame stalk, flax stalk, a kind of or wherein several combination in bluish dogbane stalk, jute stalk, hemp stalk, flax stalk, cotton stalk, sugarcane stem, tobacco stalk and the melon and fruit stalk.Other is identical with embodiment one.
When the present embodiment crop material is composition, press between the various compositions arbitrarily than combination.
Embodiment four: what present embodiment and embodiment one were different is that described polyisocyanates is poly methylene poly phenyl poly isocyanate, tolylene diisocyanate, ditan-4,4-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate and 4, a kind of or wherein several combination in the 4-dicyclohexyl methane diisocyanate.Other is identical with embodiment one.
When the present embodiment polyisocyanates is composition, press between the various compositions arbitrarily than combination.
Embodiment five: present embodiment and embodiment one are different is that described isocyanic ester performed polymer is that mol ratio by ester group and hydroxyl is that 1.1～15: 1 polyvalent alcohol and polyisocyanate mixtures obtain at 30～90 ℃ of reaction 0.5～3h, wherein polyvalent alcohol is polyether glycol or polyester polyol, wherein polyvalent alcohol is polyether glycol or polyester polyol, and polyether glycol is the polyoxyethylene enediol, the polyoxyethylene triol, polyoxypropyleneglycol, the polyoxytrimethylene triol, polytetrahydrofuran diol, the polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol, the polyether glycol of urethane is produced in tetrahydrofuran (THF)-propylene oxide copolymerization triol or commercially available being used to; Polyester polyol be polyethylene glycol adipate, poly-oneself 1,4-diacid butanediol ester, the poly-hexanodioic acid of poly-hexanodioic acid 1,3 butylene glycol ester, polydiethylene glycol adipate, poly-hexanodioic acid pentadiol ester, poly-hexanodioic acid trihydroxymethylpropanyl ester or poly-hexanodioic acid glyceryl ester.Other is identical with embodiment one.
Embodiment six: what present embodiment and embodiment one were different is described crop straw-polyurethane foam composite material, it is characterized in that described kicker is triethylene diamine, two-(dimethylaminoethyl) ether, trolamine, dimethylethanolamine, N-methylmorpholine, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, N, a kind of or wherein several combination in N-lupetazin, pentamethyl-triethylene diamine, N,N-Dibenzylamine, Tetramethyl Ethylene Diamine, stannous octoate and the dibutyltin dilaurate.Other is identical with embodiment one.
When the present embodiment kicker is composition, press between the various compositions arbitrarily than combination.
Embodiment seven: what present embodiment and embodiment one were different is that described suds-stabilizing agent is silicone oil or modified silicon oil.Other is identical with embodiment one.
Embodiment eight: what present embodiment and embodiment one were different is that described whipping agent is methylene dichloride, trichloromethane, acetone or pentane.Other is identical with embodiment one.
Embodiment nine: present embodiment and embodiment one are different is that crop straw-polyurethane foam composite material comprises that by weight 51～70 parts of crop materials, 6～20 parts of polyisocyanates or isocyanic ester performed polymer, 0.05～0.7 part of water, 0.04～0.2 part of kicker, 0.06～0.3 part of suds-stabilizing agent and 0.02～4 part of whipping agent make.Other is identical with embodiment one.
Embodiment ten: present embodiment and embodiment one are different is that crop straw-polyurethane foam composite material comprises that by weight 71～99 parts of crop materials, 21～39 parts of polyisocyanates or isocyanic ester performed polymer, 0.75～0.79 part of water, 0.21～0.39 part of kicker, 0.31～0.59 part of suds-stabilizing agent and 4.1～7.9 parts of whipping agents make.Other is identical with embodiment one.
Embodiment 11: present embodiment and embodiment one are different is that crop straw-polyurethane foam composite material comprises that by weight 90 parts of crop materials, 20 parts of polyisocyanates or isocyanic ester performed polymer, 9 parts of polyether glycols, 0.25 part of water, 0.1 part of triethylene diamine catalyzer, 0.3 part of polyether modified silicon oil suds-stabilizing agent and 5 parts of methylene dichloride whipping agents make.
Embodiment 12: what present embodiment and embodiment one were different is that crop straw-polyurethane foam composite material comprises 80 parts of crop materials, 10 parts of ditans-4 by weight, and 4-vulcabond, 4 parts of polyether glycols, 0.15 part of water, 0.06 part of dimethyl ethanolamine catalyst, 0.15 part of polyether modified silicon oil suds-stabilizing agent and 1.5 parts of pentane foaming agents are made.
Embodiment 13: present embodiment and embodiment one are different is that crop straw-polyurethane foam composite material comprises that by weight 49 parts of crop materials, 40 parts of isocyanic ester performed polymers, 14 parts of polyether glycols, 0.8 part of water, 0.3 part of DABCO BL-11 polyurethane foam catalyzer, 0.5 part of polyether modified silicon oil suds-stabilizing agent, 5 parts of FHC-2000 polyurethane foams make.
Embodiment 14: the preparation method of crop straw-polyurethane foam composite material is as follows in the present embodiment: one, be that crop material particle below the 30mm is placed in the forming mould of shaper with 50～100 weight part length, make the volume compression of particle reduce 1%～20%, the volume after the fixing compression; Two, under the room temperature in the foam box of shaper, add 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight and stir and make mixture; Three, the forming mould of crushed straw aggregate and the foam box Butt sealing in the step 2 will be held in the step 1, and the gauze of adjusting forming mould bottom just contacts the top of mixture in the foam box, behind foamable reaction 1～30min, at room temperature place ageing 1～24h, in forming mould, promptly get crop straw-polyurethane foam composite material.
Making mixture by water, kicker, suds-stabilizing agent, whipping agent and polyisocyanates or the stirring of isocyanic ester performed polymer in the present embodiment step 2 is exactly polyurathamc, and its final reaction product is a polyurethane foam; Polyurethane foam in the present embodiment step 3 in the foam box makes in the continuous forming mould that enters shaper that expands of polyurethane foam, fills all spaces in the crop material particle, and crushed straw aggregate is sticked together by means of the foaming and intumescing power of self.
Embodiment 15: what present embodiment and embodiment 14 were different is to have added 0.01～14.5 part of polyether glycol in the step 2 in the foam box of shaper by weight, and polyether glycol is polyoxyethylene enediol, polyoxyethylene triol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.Other is identical with embodiment 14.
Embodiment 16: what present embodiment and embodiment 14 were different is that the volume of particle does not reduce in the step 1.Other is identical with embodiment 14.
Embodiment 17: what present embodiment and embodiment 14 were different is in the step 1 51～70 weight part crop material particles to be placed in the forming mould of shaper, adds 6～20 parts of polyisocyanates or isocyanic ester performed polymer, 0.05～0.7 part of water, 0.04～0.2 part of kicker, 0.06～0.3 part of suds-stabilizing agent and 0.02～4 part of whipping agent in the step 2.Other is identical with embodiment 14.
Embodiment 18: what present embodiment and embodiment 14 were different is in the step 1 71～99 weight part crop material particles to be placed in the forming mould of shaper, adds 21～39 parts of polyisocyanates or isocyanic ester performed polymer, 0.75～0.79 part of water, 0.21～0.39 part of kicker, 0.31～0.59 part of suds-stabilizing agent and 4.1～7.9 parts of whipping agents in the step 2.Other is identical with embodiment 14.
Embodiment 19: what present embodiment and embodiment 14 were different is in the step 1 90 weight part crop material particles to be placed in the forming mould of shaper, adds 20 parts of polyisocyanates or isocyanic ester performed polymer, 9 parts of polyether glycols, 0.25 part of water, 0.1 part of triethylene diamine catalyzer, 0.3 part of polyether modified silicon oil suds-stabilizing agent and 5 parts of methylene dichloride whipping agents in the step 2.Other is identical with embodiment 14.
Embodiment 20: what present embodiment and embodiment 14 were different is in the step 1 80 weight part crop material particles to be placed in the forming mould of shaper, add 10 parts of ditans-4,4-vulcabond, 4 parts of polyether glycols, 0.15 part of water, 0.06 part of dimethyl ethanolamine catalyst, 0.15 part of polyether modified silicon oil suds-stabilizing agent and 1.5 parts of pentane foaming agents in the step 2.Other is identical with embodiment 14.
Embodiment 21: what present embodiment and embodiment 14 were different is in the step 1 49 weight part crop material particles to be placed in the forming mould of shaper, adds 40 parts of isocyanic ester performed polymers, 14 parts of polyether glycols, 0.8 part of water, 0.3 part of DABCO BL-11 polyurethane foam catalyzer, 0.5 part of polyether modified silicon oil suds-stabilizing agent, 5 parts of FHC-2000 polyurethane foams in the step 2.Other is identical with embodiment 14.
Used DABCO BL-11 polyurethane foam catalyzer is the commercially available kicker product that the production polyurethane foam is used in the present embodiment, and the FHC-2000 polyurethane foams is the commercially available whipping agent product that the production polyurethane foam is used.
Claims (10)
1, a kind of crop straw-polyurethane foam composite material is characterized in that crop straw-polyurethane foam composite material mainly made by 50～100 parts of crop materials, 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight.
2, crop straw-polyurethane foam composite material according to claim 1, it is characterized in that crop straw-polyurethane foam composite material also comprises 0.01～14.5 part of polyether glycol by weight, polyether glycol is polyoxyethylene enediol, polyoxyethylene triol, polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.
3, crop straw-polyurethane foam composite material according to claim 1, it is characterized in that described crop material is rice straw, wheat straw, corn stalk, sorghum stalk, soybean stalk, mung bean stalk, broad bean stalk, pea stalk, sweet potato vine, potato vine, Ipomoea batatas rattan, peanut stalk, rape stalk, sesame stalk, flax stalk, a kind of or wherein several combination in bluish dogbane stalk, jute stalk, hemp stalk, flax stalk, cotton stalk, sugarcane stem, tobacco stalk and the melon and fruit stalk.
4, crop straw-polyurethane foam composite material according to claim 1, it is characterized in that described polyisocyanates is poly methylene poly phenyl poly isocyanate, tolylene diisocyanate, ditan-4,4-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, Methylcyclohexyl diisocyanate and 4, a kind of or wherein several combination in the 4-dicyclohexyl methane diisocyanate.
5, crop straw-polyurethane foam composite material according to claim 1, it is characterized in that described isocyanic ester performed polymer is that mol ratio by ester group and hydroxyl is that 1.1～15: 1 polyvalent alcohol and polyisocyanate mixtures obtain at 30～90 ℃ of reaction 0.5～3h, wherein polyvalent alcohol is polyether glycol or polyester polyol.
6, crop straw-polyurethane foam composite material according to claim 1, it is characterized in that described kicker is triethylene diamine, two-(dimethylaminoethyl) ether, trolamine, dimethylethanolamine, N-methylmorpholine, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, N, a kind of or wherein several combination in N-lupetazin, pentamethyl-triethylene diamine, N,N-Dibenzylamine, Tetramethyl Ethylene Diamine, stannous octoate and the dibutyltin dilaurate.
7, crop straw-polyurethane foam composite material according to claim 1 is characterized in that described suds-stabilizing agent is silicone oil or modified silicon oil.
8, crop straw-polyurethane foam composite material according to claim 1 is characterized in that described whipping agent is methylene dichloride, trichloromethane, acetone or pentane.
9, the method for preparing the described crop straw-polyurethane foam composite material of claim 1, the preparation method who it is characterized in that crop straw-polyurethane foam composite material is as follows: one, be that crop material particle below the 30mm is placed in the forming mould of shaper with 50～100 weight part length, make the volume compression of particle reduce 1%～20%, the volume after the fixing compression; Two, under the room temperature in the foam box of shaper, add 5～40 parts of polyisocyanates or isocyanic ester performed polymer, 0.04～0.8 part of water, 0.03～0.4 part of kicker, 0.05～0.6 part of suds-stabilizing agent and 0.01～8 part of whipping agent by weight and stir and make mixture; Three, the forming mould of crushed straw aggregate and the foam box Butt sealing in the step 2 will be held in the step 1, and the gauze of adjusting forming mould bottom just contacts the top of mixture in the foam box, behind foamable reaction 1～30min, at room temperature place ageing 1～24h, in forming mould, promptly get crop straw-polyurethane foam composite material.
10, the preparation method of crop straw-polyurethane foam composite material according to claim 9, it is characterized in that having added 0.01～14.5 part of polyether glycol in the step 2 by weight in the foam box of shaper, polyether glycol is the polyoxyethylene enediol, the polyoxyethylene triol, polyoxypropyleneglycol, the polyoxytrimethylene triol, polytetrahydrofuran diol, the polytetrahydrofuran triol, ethylene oxide-propylene oxide copolymerization glycol, ethylene oxide-propylene oxide copolymerization triol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol or tetrahydrofuran (THF)-propylene oxide copolymerization triol.
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| CN101898399A (en) * | 2010-07-23 | 2010-12-01 | 深圳市美盈森环保科技股份有限公司 | Technology for preparing composite package cushioning material from rice straw fibers |
| CN104341770A (en) * | 2013-07-25 | 2015-02-11 | 晋江凯基高分子材料有限公司 | Preparation technology of novel environmentally friendly polyurethane foamed plastic |
| CN105350711A (en) * | 2015-11-26 | 2016-02-24 | 安徽继宏环保科技有限公司 | Heat-insulating fireproof colored steel sandwich corner plate adopting mixed straw foaming and manufacturing process thereof |
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| CN107158445A (en) * | 2012-05-29 | 2017-09-15 | 3M创新有限公司 | Absorbent article including foam of polymers and intermediate |
| CN104341770A (en) * | 2013-07-25 | 2015-02-11 | 晋江凯基高分子材料有限公司 | Preparation technology of novel environmentally friendly polyurethane foamed plastic |
| CN105350711A (en) * | 2015-11-26 | 2016-02-24 | 安徽继宏环保科技有限公司 | Heat-insulating fireproof colored steel sandwich corner plate adopting mixed straw foaming and manufacturing process thereof |
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