CN107033327B - High-compression-resistance polyurethane composite material for ground of refrigeration house and preparation method thereof - Google Patents
High-compression-resistance polyurethane composite material for ground of refrigeration house and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/12—Flooring or floor layers made of masses in situ, e.g. seamless magnesite floors, terrazzo gypsum floors
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Abstract
The invention belongs to the technical field of polyurethane, and particularly relates to a high-pressure-resistant polyurethane composite material for a refrigeration house ground and a preparation method thereof. According to the invention, through effective collocation of phthalic anhydride polyester and amine ether, the phthalic anhydride polyester and the amine ether react with polymethylene polyphenyl polyisocyanate, a rigid benzene ring structure and a highly symmetrical structure are introduced into a molecular chain, so that higher mechanical strength of foam is achieved, and meanwhile, excessive isocyanic acid radical generates a PIR structure through induction of a catalyst, so that good dimensional stability at low temperature is realized, and the requirement of high compressive strength is met; A. the component B is sprayed on site by adopting high-pressure spraying equipment, compared with paving and pasting XPS, the construction machine is simple, continuous construction is realized, a seamless connection heat insulation system is formed, gap correction is not needed, foam is stable, density is uniform, heat insulation performance is good, and construction time is saved.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a high-pressure-resistant polyurethane composite material for a refrigeration house ground and a preparation method thereof.
Background
With the rapid development of Chinese economy and the increasing improvement of consumer quality, the annual increase of the refrigerator in the next 10 years reaches more than 30%, and the construction of the refrigerator in China is in the beginning stage. In the traditional design and construction process of a refrigeration house, the bearing design of the ground generally requires more than or equal to 350KPa, some of the bearing design even reaches 500KPa, and is trapped in the current situation that the compressive strength of polyurethane foam is lower, and in order to meet the requirement of the cargo carrying walking of transport vehicles such as forklifts, the ground which can preserve heat and bear the load is mostly paved layer by adopting polystyrene extruded sheets (XPS). The heat insulation performance of the XPS plate is poorer than that of polyurethane foam, a gap formed by layer-by-layer paving has a cold bridge hidden danger, a certain gap correction coefficient is required to assist, and meanwhile, the existence of the gap is beneficial to the permeation of small molecular water vapor, so that the phenomenon of 'cold running' is frequently caused.
The prior patent CN104672420 'a high-strength polyurethane rigid foam, a preparation method and application thereof' discloses a technology with the compressive strength reaching 200KPa, which is far from reaching the ground use requirement of a refrigeration house, and the prior rigid polyurethane foam has the density of a common finished product (30-50 kg/m)3) No report that the compressive strength reaches more than or equal to 350KPa is found.
At the present stage, a polyurethane material which has low cost, has compressive strength meeting the design requirement of the refrigeration storage (more than or equal to 350KPa) and realizes seamless connection is urgently needed for the refrigeration storage ground in the refrigeration storage construction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-pressure-resistant polyurethane composite material for the ground of a refrigeration house and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a high compression-resistant polyurethane composite material for a ground of a refrigeration house is formed by mixing a component A and a component B according to the weight ratio of 1: 1;
wherein, the component A comprises the following components in parts by weight: 15-25 parts of polyether polyol, 35-45 parts of polyester polyol, 1-1.5 parts of foam stabilizer, 0.5-1 part of chemical foaming agent, 10-20 parts of physical foaming agent, 5-10 parts of catalyst and 15-20 parts of flame retardant;
the component B is polymethylene polyphenyl polyisocyanate.
The preparation method of the high-pressure-resistant polyurethane composite material for the ground of the refrigeration house comprises the following steps:
(1) adding 15-25 parts of polyether polyol and 35-45 parts of polyester polyol into a reaction kettle, adding 1-1.5 parts of foam stabilizer, 0.5-1 part of chemical foaming agent, 10-20 parts of physical foaming agent, 5-10 parts of catalyst and 15-20 parts of flame retardant, and stirring for 0.5-1h at 20-25 ℃ to obtain a component A;
(2) taking polymethylene polyphenyl polyisocyanate as a component B, uniformly mixing the component A and the component B in the step (1) according to the weight ratio of 1:1, and mixing and spraying the mixture on the ground of a refrigeration house by a high-pressure spraying machine for foaming and forming.
The invention has the beneficial effects that:
1. the invention effectively matches phthalic anhydride polyester and amine ether, reacts with polymethylene polyphenyl polyisocyanate, introduces a rigid benzene ring structure and a highly symmetrical structure into a molecular chain, achieves higher mechanical strength of foam, and simultaneously generates a PIR structure by inducing excessive isocyanic acid radical through a catalyst, thereby achieving good dimensional stability at low temperature and achieving the requirement of high compressive strength.
2. The component A is produced at normal temperature, so that energy is saved, equipment loss is reduced, and complicated operation is realized; A. the component B is sprayed on site by adopting high-pressure spraying equipment, compared with paving and pasting XPS, the construction machine is simple, continuous construction is realized, a seamless connection heat insulation system is formed, gap correction is not needed, foam is stable, density is uniform, heat insulation performance is good, and construction time is saved. The ground use of the cold storage can reach the following indexes through detection, and the indexes completely reach the regulations of relevant standards:
further, the polyether polyol is ethylenediamine polyol, the viscosity is 30000-50000 MPa-s/25 ℃, and the hydroxyl value is 700-800 mgKOH/g; the polyester polyol is aromatic dibasic acid polyol, the viscosity is 6000-15000 MPa-s/25 ℃, the hydroxyl value is 170-320mgKOH/g, and the acid value is less than or equal to 1 mgKOH/g.
Furthermore, the polyether polyol is bignonized stock BH403, Hebei Asia east chemical YD403, Lanxindongda DD403 or new Tanshun material NJ 403; the polyester polyol is Spandex PS3152, Spandex PS2412 or Nanguan chemical NG 8535.
The further scheme has the beneficial effects that phthalic anhydride, aromatic dibasic acid polyol PS3152 and ethylenediamine polyol BH403 are matched, a PIR structure and a PUR structure are effectively combined, high-degree symmetry and high-content rigid benzene rings in the structure are utilized, high foam mechanical strength is achieved, meanwhile, the high-activity primary hydroxyl polyester polyol and the amine ether with the autocatalysis effect are particularly suitable for the high reaction speed of a refrigeration house spray coating, and the achievement of seamless connection spray coating construction and high compressive strength is effectively promoted.
Further, the foam stabilizer is a non-hydrolytic silicon-carbon surfactant.
Further, the foam stabilizer is one or more of German AK8805, Mei graph L6950, Mei graph L6920 and German AK 158.
Further, the chemical foaming agent is deionized water;
the physical foaming agent is monofluorodichloroethane or pentafluoropropane;
the catalyst is a mixture of more than two of PT303, PT304, PT306, A33, K15 or PC41 sold by air chemical company;
the flame retardant is one or a mixture of more than two of tri (chloroisopropyl) phosphate-TCPP, triethyl phosphate-TEP, trichloroethyl phosphate-TCEP or dimethyl methylphosphonate-DMMP.
Drawings
FIG. 1 is a graph showing the compression resistance in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The polyether polyol used in the embodiment of the invention is BH403 of Binghua GmbH, the polyester polyol used is PS3152 of Nanjing Sitaopan, the flame retardant used is TCPP of Shanghai Jack, the physical foaming agent used is 141b of Sanmei, Zhejiang, and the foam homogenizing agent is Mitig L6950, and the catalyst used is a product sold in the air chemical industry.
Example 1
A high compression-resistant polyurethane composite material for a ground of a refrigeration house is formed by mixing a component A and a component B according to the weight ratio of 1: 1;
wherein, the component A comprises: 22kg of polyether polyol BH403, 42kg of polyester polyol PS3152, 1.2kg of foam stabilizer L6950, 0.5kg of deionized water, 13kg of physical foaming agent 141b, 2kg of catalytic PT303, 1.8kg of catalyst PT304, 1.6kg of catalyst K15, 0.9kg of catalyst A33 and 15kg of flame retardant TCPP;
the component B is 100kg of polymethylene polyphenyl polyisocyanate.
The preparation method of the high-pressure-resistant polyurethane composite material for the ground of the refrigeration house comprises the following steps:
(1) adding 22kg of polyether polyol BH403 and 42kg of polyester polyol PS3152 into a reaction kettle, adding 1.2kg of foam stabilizer L6950, 0.5kg of deionized water, 13kg of physical foaming agent 141b, 2kg of catalytic PT303, 1.8kg of catalyst PT304, 1.6kg of catalyst K15, 0.9kg of catalyst A33 and 15kg of flame retardant TCPP, and stirring for 0.5-1h at 20-25 ℃ to obtain a component A;
(2) taking polymethylene polyphenyl polyisocyanate as a component B, uniformly mixing the component A and the component B in the step (1) according to the weight ratio of 1:1, and mixing and spraying the mixture on the ground of a refrigeration house by a high-pressure spraying machine for foaming and forming.
The high-pressure polyurethane foam thermal insulation material is sprayed on the ground of a refrigeration house by a Gurueli A25 spraying device under high pressure, and the high-pressure polyurethane foam thermal insulation material is prepared by layer-by-layer spraying construction, wherein the indexes of the tested product are as follows:
| test product | High compression resistant polyurethane foam |
| Product oxygen index (%) | 26.4 |
| Density of the product (kg/m)3) | 46.8 |
| Compressive Strength (KPa) | 403 |
| Sample closed cell fraction (%) | 91.33 |
| Sample high temperature dimensional stability (%) | 0.47*0.58*0.33 |
| Sample Low temperature dimensional stability (%) | 0.26*0.37*0.21 |
| Coefficient of thermal conductivity (w/m.k) | 0.02186 |
Example 2
A high compression-resistant polyurethane composite material for a ground of a refrigeration house is formed by mixing a component A and a component B according to the weight ratio of 1: 1;
wherein, the component A comprises: 15kg of polyether polyol BH403, 35kg of polyester polyol PS3152, 1.0kg of foam stabilizer L6950, 1.5kg of deionized water, 20kg of physical foaming agent 141b, 2kg of catalytic PT303, 2kg of catalyst PT304, 3kg of catalyst K15, 0.5kg of catalyst A33 and 20kg of flame retardant TCPP;
the component B is 100kg of polymethylene polyphenyl polyisocyanate.
The preparation method of the high-pressure-resistant polyurethane composite material for the ground of the refrigeration house comprises the following steps:
(1) adding 15kg of polyether polyol BH403 and 35kg of polyester polyol PS3152 into a reaction kettle, adding 1.0kg of foam stabilizer L6950, 1.5kg of deionized water, 20kg of physical foaming agent 141b, 2kg of catalytic PT303, 2kg of catalyst PT304, 3kg of catalyst K15, 0.5kg of catalyst A33 and 20kg of flame retardant TCPP, and stirring for 0.5-1h at the temperature of 20-25 ℃ to obtain a component A;
(2) taking polymethylene polyphenyl polyisocyanate as a component B, uniformly mixing the component A and the component B in the step (1) according to the weight ratio of 1:1, and mixing and spraying the mixture on the ground of a refrigeration house by a high-pressure spraying machine for foaming and forming.
And spraying the polyurethane foam on the ground of a refrigeration house at high pressure by a Gurueli A25 spraying device, and performing layer-by-layer spraying construction to prepare the high-pressure-resistant polyurethane foam heat-insulating material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A high compression-resistant polyurethane composite material for a ground of a refrigeration house is characterized by being prepared by mixing a component A and a component B according to the weight ratio of 1: 1;
the component A comprises, by weight, 15-25 parts of polyether polyol, 35-45 parts of polyester polyol, 1-1.5 parts of foam stabilizer, 0.5-1 part of chemical foaming agent, 10-20 parts of physical foaming agent, 5-10 parts of catalyst and 15-20 parts of flame retardant;
the component B is polymethylene polyphenyl polyisocyanate;
the polyether polyol is ethylenediamine polyol which is bigami BH403 or Hebei Asia east chemical YD 403;
the polyester polyol is aromatic dibasic acid polyol which is Spilan PS 3152;
the physical foaming agent is monofluorodichloroethane or pentafluoropropane;
the flame retardant is one or a mixture of more than two of tri (chloroisopropyl) phosphate-TCPP, triethyl phosphate-TEP, trichloroethyl phosphate-TCEP or dimethyl methyl phosphonate-DMMP;
the catalyst is one or more of PT303, PT306 or A33 and one or more of PT304, K15 or PC 41.
2. The high pressure resistant polyurethane composite material for the ground of the refrigeration house according to claim 1, wherein the foam stabilizer is a non-hydrolytic silicon-carbon surfactant.
3. The high pressure resistant polyurethane composite material for freezer floors as claimed in claim 2, wherein the foam stabilizer is one or more of german AK8805, maghemin L6950, maghemin L6920 or german AK 158.
4. The high pressure resistant polyurethane composite material for the ground of the refrigeration house according to claim 1, wherein the chemical foaming agent is deionized water.
5. The preparation method of the high-pressure-resistant polyurethane composite material for the ground of the refrigeration house according to any one of claims 1 to 4, which is characterized by comprising the following steps of:
(1) adding 15-25 parts of polyether polyol and 35-45 parts of polyester polyol into a reaction kettle, adding 1-1.5 parts of foam stabilizer, 0.5-1 part of chemical foaming agent, 10-20 parts of physical foaming agent, 5-10 parts of catalyst and 15-20 parts of flame retardant, and stirring for 0.5-1h at 20-25 ℃ to obtain a component A;
(2) taking polymethylene polyphenyl polyisocyanate as a component B, uniformly mixing the component A and the component B in the step (1) according to the weight ratio of 1:1, and mixing and spraying the mixture on the ground of a refrigeration house by a high-pressure spraying machine for foaming and forming.
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| CN109294214B (en) * | 2018-09-26 | 2021-12-07 | 上海东大聚氨酯有限公司 | Conjugate polyether, polyurethane raw material composition, polyurethane thermal insulation material derived from conjugate polyether, and preparation method and application of polyurethane thermal insulation material |
| CN109942789A (en) * | 2019-02-25 | 2019-06-28 | 广州立泰新材料科技有限公司 | A kind of high strength hard polyurethane foam and preparation method thereof |
| CN110330621A (en) * | 2019-08-07 | 2019-10-15 | 河南铎润新材料有限公司 | A kind of polyurethane foamed material and its manufactured cold storage plate with high fire-retardance effect |
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| CN106167541B (en) * | 2016-08-01 | 2019-03-15 | 山东一诺威新材料有限公司 | Continous way produces PIR bulk bubble combined polyether and its preparation method and application |
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| CN101798377A (en) * | 2010-03-24 | 2010-08-11 | 山东东大聚合物股份有限公司 | Environment-friendly composite applicable to pipeline heat insulation and preparation method thereof |
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| CN104877105A (en) * | 2015-04-24 | 2015-09-02 | 黎明化工研究设计院有限责任公司 | Polyurethane hard foam composite material and preparation method thereof |
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