CN1119381C - Compound containing nano montmorillonoid and its prepn - Google Patents
Compound containing nano montmorillonoid and its prepn Download PDFInfo
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- CN1119381C CN1119381C CN 01109463 CN01109463A CN1119381C CN 1119381 C CN1119381 C CN 1119381C CN 01109463 CN01109463 CN 01109463 CN 01109463 A CN01109463 A CN 01109463A CN 1119381 C CN1119381 C CN 1119381C
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Abstract
The present invention discloses a nanometer montmorillonite / polyether alcohol or polyester alcohol compound. The compound containing nanometer montmorillonite comprises components with the following proportion by weight: 100 portions of polyether alcohol or polyester alcohol monomers, 0.1 to 40 portions of nanometer montmorillonitic clay and 0.4 to 20 portions of intercalator. The present invention also discloses a preparation method for the compound. The compound is synthesized on the basis of raw materials of nanometer polyurethane composite materials, and can be directly applied to the existing synthesizing and processing field of the polyurethane. The compound can be directly applied to the solution polymerization, such as polyurethane fibers, paint, adhesive agents and other elastomer, without changing the existing operating processes and synthesizing paths and adding any device, and can be used for the fusion polymerization after the vacuum drying is carried out.
Description
The present invention relates to a kind of compound containing nano montmorillonoid, relate in particular to a kind of nano imvite/Aethoxy Sklerol or polyesterols mixture, the invention still further relates to the preparation method of this mixture.
Synthetic and the processing that nano montmorillonite is applied to polymkeric substance is a kind of material science and technology that just rose in recent years.Because the particle diameter of nano montmorillonite in matrix material can reach 10～30 nanoscales, has very large interfacial area, nano montmorillonite disperse phase and polymer-based carbon body interface have the ideal adhesiveproperties, the thermal expansivity of these two kinds of material matrix is complementary, and can give full play to the excellent mechanical property of nano inorganic material intrinsic, high heat resistance energy.
About the matrix material of nanoclay, existing many achievements in research have been declared patented invention.Chinese patent CN1138593A and CN1206028A utilize in-situ inserted polymerization to be equipped with nanometer composite polyamide-clay material, have higher molecular weight and narrower molecular weight distribution, and mechanical strength, Young's modulus and heat-drawn wire improve.The matrix material that nanoclay is all arranged as polystyrene, polyester, nylon, rubber etc. in addition, the adding of nanoclay inorganic materials, make material property significantly be improved, also improved processing characteristics simultaneously, as patent CN1242392A, CN1242393A, CN1238353A etc.
It is few that nanoclay is scattered in the research report that is used to strengthen the polyurethane material performance in the polyurethane matrix.External research article (the Zhen Wang of report the earliest, Thomas J.Pinnavaia.Chem.Mater.1998,10,3769～3771) show that elastic polyurethane/clay nanocomposites has the enhancement of mechanical property, its synthetic method is to have the organic clay of chainextender directly to mix with ginseng the prepolymer of methylenediphenyl diisocyanates difunctionality.Adding for the nanometer lamella, when improving the polyurethane elastomer modulus, improve its intensity and toughness again significantly, this phenomenon is different from fully sacrifices behavior (Woods, the G.the ICI Polyurethane Book of mechanical property when adding inorganic materials for reducing cost in the past; John Wiley ﹠amp; Sons; New York, 1990).The author thinks, the raising of intensity and modulus, complete enhancement owing to the nanometer silicon chip that is scattered in system, and elastic improvement, part can be owing to the plastification of complex cation in the clay layer structure, because it makes polymkeric substance form suspension chain on matrix and the conformation behavior of polymkeric substance is exerted an influence.
Taiwan's scholars is also delivered the synthetic of one piece of relevant nanoclay urethane and characterized on polymer magazine in 2000 article (T.-K.Chen, et al.Polymer 2,000 41 1345～1353), he directly mixes organic clay in solution with urethane, the nano level clay of the very difficult assurance of this method overcomes huge surface force and is uniformly dispersed under the effect of mechanical force.
People such as Kosinski have reported a kind of sheet clay compound polyurethane fiber and film among the patent WO97/49847 in 1997.But its objective is dyeability and the detergency of improving polyurethane fiber and film, and when keeping its excellent resilience performance, improve the processing characteristics of urethane.This invention is at wet-spinning and dry-spinning and polyurethane film-forming field, in this invention, in water, add various dissimilar cats products and handle clays, and then precipitation, filter, oven dry, pulverize, obtain particle diameter at last less than 3 microns clay particle.With the urethane compound tense, stir by high speed shear and to make clay dispersion in dimethylacetamide solution, mix stirring with the urethane that is dissolved in N,N-DIMETHYLACETAMIDE in advance according to a certain percentage, become spinning or film forming stoste.
Above research and patent are that the synthetic and processing of clay nano polyurethane material has proposed proper explanations and method, but only are at specific purpose, in practical application in industry, and troublesome poeration, cost height.
The raw material that the objective of the invention is to be based on the nano-polyurethane matrix material is synthetic, a kind of nano imvite/Aethoxy Sklerol or polyesterols mixture are provided, it can directly apply to the synthetic and manufacture field of existing urethane, do not change existing operating procedure and synthetic route, need not add any equipment.
Another object of the present invention is to provide the preparation method of a kind of nano imvite/Aethoxy Sklerol or polyesterols mixture.
A kind of nano imvite/Aethoxy Sklerol or polyesterols mixture comprise following component by weight: 100 parts of Aethoxy Sklerol or polyesterols monomers; 0.1～40 part of nano montmorillonite clay is preferably 1-20 part; 0.4～20 part of intercalator.Described nano montmorillonite clay size is 10～30 nanometers, and described clay is for containing 85～93% montmorillonite silico-aluminates, and particle diameter is 30～80 microns, and cation exchange capacity is 50～200 milligramequivalents/per 100 gram soil, and the clay seam spacing is 2～6 .Described Aethoxy Sklerol is molecular weight M=1.0 * 10
3～1.0 * 10
5Polytetramethylene ether glycol, polypropylene oxide glycol, polyoxyethylene oxypropylene copolyether glycol, tetrahydrofuran (THF)-propylene oxide binary copolymerization ether glycol, tetrahydrofuran (THF)-propylene oxide-oxyethane terpolymer ether glycol or be raw material synthetic polyfunctional group polyethers with the glycerine of trifunctional.Described polyesterols is molecular weight M=1.0 * 10
3～1.0 * 10
5The multipolymer, Viscotrol C, the poly-epsilon-caprolactone glycol that form by hexanodioic acid or Tetra hydro Phthalic anhydride and ethylene glycol, propylene glycol, butyleneglycol, glycerine.Described intercalator is chain alkyl quaternary amine, nylon salt etc., preferred C16-18 alkyl quaternary amine salt.Aethoxy Sklerol and polyesterols raw material that the present invention adopts can be the commercially available prod.
The preparation method of a kind of nano imvite/Aethoxy Sklerol of the present invention or polyesterols mixture in turn includes the following steps by weight:
A, be 50～200 milligramequivalents/per, 100 gram soil with cation exchange capacity, the clay seam spacing is that 0.1～40 part of the clay of 2～6 is that 60～80 ℃ water high speed stirs 30～1000 parts of temperature, ultra-sonic oscillation 0.5-2 hour, form stable suspension system, left standstill aquation 20-48 hour.
B, intercalator is dissolved in 5～20 parts of water for 0.4～20 part, join in the above-mentioned clay suspension system, at 60～90 ℃ of following high-speed stirring 2-4 hours, ultra-sonic oscillation 0.5-2 hour.
C, molecular weight are 1.0 * 10
3～1.0 * 10
5Aethoxy Sklerol or polyesterols be dissolved in 300～1000 parts of N for 100 parts, in N '-dimethyl formamide, under 80～100 ℃ and high-speed stirring, add above-mentioned clay suspension system, high-speed stirring 2-10 hour and ultra-sonic oscillation 0.5-2 hour, continue to be heated to the detection moisture content and be lower than till 0.05%.
A kind of nano imvite/Aethoxy Sklerol of the present invention or polyesterols mixture can directly apply to solution polymerization, and be synthetic as spandex silk, coating, tackiness agent and other elastomerics; Can also be used for the scorification polymerization after the vacuum-drying.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1:
Clay 2 grams that with cation exchange capacity are 100 milligramequivalents/per, 100 gram soil are that 60～80 ℃ water high speed stirs in 300 gram temperature, ultra-sonic oscillation half an hour form stable suspension system, leave standstill aquation 24 hours.Intercalator 5 gram is dissolved in 40 gram water, join in the above-mentioned clay suspension system, 60～90 ℃ of following high-speed stirring 3 hours, ultra-sonic oscillation half an hour.Molecular weight is that 2000 polytetrahydrofuran diol, 100 grams are dissolved in 1000 gram N, in N '-dimethyl formamide, under 80～100 ℃ and high-speed stirring, add above-mentioned clay suspension system, high-speed stirring 4 hours and ultra-sonic oscillation half an hour, continue to be heated to the detection moisture content and be lower than till 0.05%, the content of nanoclay is 1.9% (weight) in the product.
Embodiment 2～5:
Clay content is respectively: 5 grams, 8 grams, 13 grams, 16 grams, other conditions are with embodiment 1.The content of nanoclay is (weight) 4.5%, 7.1%, 11.0%, 13.2% in the product.
Embodiment 6:
Clay 2 grams that with cation exchange capacity are 100 milligramequivalents/per, 100 gram soil are that 60～80 ℃ water high speed stirs in 900 gram temperature, ultra-sonic oscillation half an hour form stable suspension system, leave standstill aquation 24 hours.Intercalator 5 gram is dissolved in 60 gram water, join in the above-mentioned clay suspension system, 60～90 ℃ of following high-speed stirring 3 hours, ultra-sonic oscillation half an hour.Molecular weight is that 2000 polyethylene glycol adipate, 150 grams are dissolved in 1500 gram N, in N '-dimethyl formamide, under 80～100 ℃ and high-speed stirring, add above-mentioned clay suspension system, high-speed stirring 4 hours and ultra-sonic oscillation half an hour, continue to be heated to the detection moisture content and be lower than till 0.05%, the content of nanoclay is 1.3% (weight) in the product.
Embodiment 7～10:
It is 5 grams, 9 grams, 13 grams, 17 grams that the clay dosage is respectively, and other conditions are with embodiment 6.The content of nanoclay is (weight) 3.1%, 5.5%, 7.7%, 9.8% in the product.
Embodiment 11～13:
Other conditions are with embodiment 8, and only molecular weight is that 2000 polyethylene glycol adipate is in the Change Example: molecular weight is that 2000 polypropylene glycol, molecular weight are 2000 poly-epsilon-caprolactone glycol, the poly-adipate glycol butanediol ester of molecular weight 2000.Product is 5.5% dissimilar polyethers or polyester glycol for nanoclay content.
Claims (4)
1. a compound containing nano montmorillonoid comprises following component: 100 parts of Aethoxy Sklerol or polyesterols monomers, 0.1～40 part of nano montmorillonite clay, 0.4～20 part of intercalator by weight;
Described nano montmorillonite clay size is 10～30 nanometers, and described clay is for containing 85～93% montmorillonite silico-aluminates, and particle diameter is 30～80 microns, and cation exchange capacity is 50～200 milligramequivalents/per 100 gram soil, and the clay seam spacing is 2～6 ;
Described Aethoxy Sklerol is molecular weight M=1.0 * 10
3～1.0 * 10
5Polytetramethylene ether glycol, polypropylene oxide glycol, polyoxyethylene oxypropylene copolyether glycol, tetrahydrofuran (THF)-propylene oxide binary copolymerization ether glycol, tetrahydrofuran (THF)-propylene oxide-oxyethane terpolymer ether glycol or be raw material synthetic polyfunctional group polyethers with the glycerine of trifunctional; Described polyesterols is molecular weight M=1.0 * 10
3～1.0 * 10
5The multipolymer, Viscotrol C, the poly-epsilon-caprolactone glycol that form by hexanodioic acid or Tetra hydro Phthalic anhydride and ethylene glycol, propylene glycol, butyleneglycol, glycerine;
Described intercalator is chain alkyl quaternary amine, nylon salt.
2. according to a kind of compound containing nano montmorillonoid of claim 1, described nano montmorillonite clay is 1-20 part by weight.
3. according to a kind of compound containing nano montmorillonoid of claim 1, described intercalator is a C16-18 alkyl quaternary amine salt.
4. the preparation method of a compound containing nano montmorillonoid in turn includes the following steps by weight:
A, be 50～200 milligramequivalents/per, 100 gram soil with cation exchange capacity, the clay seam spacing is that 0.1～40 part of the clay of 2～6 is that 60～80 ℃ water high speed stirs 30～1000 parts of temperature, ultra-sonic oscillation 0.5-2 hour, form stable suspension system, left standstill aquation 20-48 hour;
B, intercalator is dissolved in 5～20 parts of water for 0.4～20 part, join in the above-mentioned clay suspension system, at 60～90 ℃ of following high-speed stirring 2-4 hours, ultra-sonic oscillation 0.5-2 hour;
C, molecular weight are 1.0 * 10
3～1.0 * 10
5Aethoxy Sklerol or polyesterols be dissolved in 300～1000 parts of N for 100 parts, in N '-dimethyl formamide, under 80～100 ℃ and high-speed stirring, add above-mentioned clay suspension system, high-speed stirring 2-10 hour and ultra-sonic oscillation 0.5-2 hour, continue to be heated to the detection moisture content and be lower than till 0.05%.
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| CN 01109463 CN1119381C (en) | 2001-03-14 | 2001-03-14 | Compound containing nano montmorillonoid and its prepn |
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| CN 01109463 CN1119381C (en) | 2001-03-14 | 2001-03-14 | Compound containing nano montmorillonoid and its prepn |
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| CN1119381C true CN1119381C (en) | 2003-08-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360611C (en) * | 2005-01-18 | 2008-01-09 | 中国科学院化学研究所 | Preparation method of nanometer montmorillonite organic phase intercalation |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314728C (en) * | 2004-02-25 | 2007-05-09 | 华南理工大学 | Nano composite of unsaturation poly-ester/active rubber/montmorllonite and preparation process thereof |
| KR20050117629A (en) * | 2004-02-28 | 2005-12-15 | 학교법인고려중앙학원 | Clay-polyurethane nano composite and method for preparing the same |
| CN100443434C (en) * | 2004-06-07 | 2008-12-17 | 华新丽华股份有限公司 | Mixture of aluminium compound and clay and its prepn process |
| CN1323118C (en) * | 2005-07-27 | 2007-06-27 | 厦门大学 | Fire-proof paint modifier of tunnel based on polymer/clay intercalation modifying technology and production thereof |
| CN100372890C (en) * | 2005-08-10 | 2008-03-05 | 北京玻钢院复合材料有限公司 | Unsaturated polyester/polyurethane/organic montmorillonite composite material and production thereof |
| CN1324084C (en) * | 2005-10-09 | 2007-07-04 | 华东理工大学 | PA/PET high molecule alloy material |
| CN101343405B (en) * | 2008-04-29 | 2011-01-12 | 常利红 | Preparation method for aliphatic polyester/phyllosilicate nano-composite material |
| CN102115577B (en) * | 2009-12-30 | 2013-07-24 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of polyester-ether elastomer/montmorillonite composite material |
| TW201638213A (en) * | 2015-04-29 | 2016-11-01 | Guo-Liang Zheng | Clay-polyurethane composite material and preparation method thereof |
| TWI547508B (en) * | 2015-05-01 | 2016-09-01 | Guo-Liang Zheng | Bridging agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100360611C (en) * | 2005-01-18 | 2008-01-09 | 中国科学院化学研究所 | Preparation method of nanometer montmorillonite organic phase intercalation |
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Assignee: Zhejiang Huafeng Spandex Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2005.10.20 to 2015.10.19 contract change Contract record no.: 2009330000215 Denomination of invention: Compound containing nano montmorillonoid and its prepn Granted publication date: 20030827 License type: Exclusive license Record date: 2009.2.9 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2005.10.20 TO 2015.10.19; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE HUAFENG SPANDEX CO., LTD. Effective date: 20090209 |
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Granted publication date: 20030827 Termination date: 20130314 |