CN101117822A - Vegetable oil radical polyurethane composite panels and continuous production method - Google Patents
Vegetable oil radical polyurethane composite panels and continuous production method Download PDFInfo
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- CN101117822A CN101117822A CNA2007100238537A CN200710023853A CN101117822A CN 101117822 A CN101117822 A CN 101117822A CN A2007100238537 A CNA2007100238537 A CN A2007100238537A CN 200710023853 A CN200710023853 A CN 200710023853A CN 101117822 A CN101117822 A CN 101117822A
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Abstract
The present invention discloses a plant oil based polyurethane compound wall plate and a related continuous production method. The surface of the thermal insulation layer of polyurethane is coated with a protection layer. The thermal insulation layer and the protection layer of polyurethane are stuck by adhesive force of polyurethane; the thermal insulation layer is plant oil based polyurethane hard bubble by the reaction of compositions A and B. The present invention has the advantages of high production efficiency, high stability of product dimensions and adhesive force.
Description
Technical field:
The present invention relates to a kind of Rigid foam polyurethane and production method.
Background technology:
In today that petroleum resources reduce day by day, save energy and reduce the cost, improve environment and become social theme.Though China's economy has obtained high speed development, the per GDP energy consumption is that the shared ratio of the several times of developed country, especially building energy consumption is bigger, has had a strong impact on development and national economy.Therefore, nation-building portion has begun to put teeth in building energy conservation.RPUF becomes the energy-saving material first-selection with plurality of advantages such as coefficient of thermal conductivity are little, has obtained using widely in building energy saving field.
Common polyurethane rigid foam plastic is that the combination material by isocyanide ester and polyalcohol forms through chemical reaction.Because the finiteness of petroleum resources, the manufacturing process of oil PPG are dangerous again complicated, cost height and contaminated environment, its price also fluctuates with the fluctuation of oil price.People begin to seek reproducible alternate resources.The application of crude vegetal class polyurethane has caused people's attention.The synthetic method of relevant vegetable oil polyol.Report is all arranged both at home and abroad.As Chinese patent " a kind of preparation method of vegetable oil polyol " publication number: CN1869184, having introduced with soybean wet goods vegetable oil is that raw material makes the polyalcohol product that has active gene through chemical reactions such as over-churnings.The domestic suitability for industrialized production that also has producer to realize vegetable oil polyol.But product all can not be as the body material synthesis of polyurethane, generally all is that a small amount of (＜20%) is added in the oil PPG and uses.If adding proportion is excessive, easily cause defectives such as polyurethane foam contraction, perforate, resistance to compression and adhesive strength reduction.Because addition is little, institute's economic benefit of bringing is limited thus.
The Rigid foam polyurethane material that is used for construction wall insulation is at present made with two kinds of methods usually, the one, in mould with polyurethane and surface layer is once-combined forms; The 2nd, viscoelastic polyurethane is attached on the foundation wall, repave with grid cloth and cement mortar and do surface layer.For example: Chinese patent " polyurethane foam one-shot forming heat-insulation wall plate and manufacture craft thereof ", publication number: CN1584254, disclose a kind of in mould finish coat and the one-time formed manufacture craft of polyurethane adhesion.The shortcoming of this method is that each molding time is bigger, and efficient is low, and labour intensity is big.Chinese patent " technological flow for producing decorative and insulating composite polyurethane slabs of wall " publication number: CN1326038 has described die methods production composite plate technology equally in the patent, and finish coat and job practices are had been described in detail.Shortcoming is that efficient is low equally, and labour intensity is big.
Summary of the invention
The object of the present invention is to provide the continuous producing method of a kind of production efficiency height, dimensional stability is good, adhesion strength is big vegetable oil radical polyurethane composite panels.
Technical solution of the present invention is:
A kind of vegetable oil radical polyurethane composite panels is characterized in that: comprise polyurethane insulation coating, and polyurethane insulation coating surface recombination topping, polyurethane insulation coating and topping are by the adhesion stress bonding of polyurethane self; Above-mentioned insulation layer is to be hard bubbled by the vegetable oil based polyurethane that A, B component hybrid reaction make, and described A component is an isocyanide ester, and the B component is to be made up of following weight item:
10～60 parts of 40～80 parts of oil PPGs of vegetable oil polyol
0～10 part of 0～30 part of crosslinking agent of PEPA
0.5～10 part of 2～5 parts of catalyzer of foam stabiliser
6～15 parts of 10～50 parts of fire retardants of blowing agent
0～2 part in water.More than each composition in container, stir and promptly form the B component.
The consumption of A component and B component (weight) forms polyurethane insulation coating than being 1: 0.7～1.3 through the chemical reaction fast foaming.
Topping is high-density fiber cement board, tile panel, plastic plate, plastic-aluminum alloy sheets or aluminium alloy plate.
Vegetable oil polyol is one or more in soybean oil polyalcohol, castor oil polyhydric alcohol, rapeseed oil polyalcohol, cottonseed oil polyalcohol, palm oil polyalcohol, the recovered oil polyalcohol.The oil PPG is one or more in glycerine, sucrose, expoxy propane PPG, sorbierite, glycerine, expoxy propane PPG, the ethylenediamine PPG.PEPA is one or more in phthalic anhydride, diethylene glycol (DEG) PEPA, the glycerine PEPA.Crosslinking agent is one or more in diethylene glycol (DEG), propane diols, the triethanolamine.Catalyzer is one or more in the rare amine of three second (33% propylene glycol solution), dimethyl amine, the triethylamine.Foam stabiliser is an organic silicon surfactant.Blowing agent is one or more in fluoro trichloromethane (CFC11), a fluorine dichloroethanes, the pentamethylene; Fire retardant is dimethyl methyl phosphonate (being called for short TCPP), three (chloro isopropyl) phosphate (being called for short DMMP), three (β-chloroethyl) phosphate (being called for short TCEP).
A kind of continuous producing method of vegetable oil radical polyurethane composite panels; it is characterized in that: on tinuous production; with the topping horizontal on conveyer belt; the topping both sides are provided with block, and the top is a plastic sheeting, with A, B two components in the high pressure casting machine is cast in the cavity of topping and plastic sheeting; repressed slaking moulding; take plastic sheeting off and form combined wall board,, carry out serialization production along with moving ahead of transmission system.
Production efficiency height of the present invention, product size good stability, adhesion strength are big, the A component is an isocyanide ester, its structural performance is stable, little to the product properties influence, the final products performance depends primarily on the influence of the interpolation of the molecular structure of each raw material among the component B and other auxiliary agent to agent structure and properties of product, wherein adding the oil PPG, mainly is to utilize it to contain the intensity that the big sucrose composition of degree of functionality has improved foam; Reduce reactivity simultaneously, prolonged gel time, improved the flowability of foam.Wherein adding benzoic anhydride polyester polyol mainly is to introduce the cyclic skeleton structure, increases the compressive strength of foam, prevents foam contraction.The adding crosslinking agent can improve the toughness of foam, prevents that the foam cracking from improving adhesive strength.Wherein catalyzer adopts nonmetallic tertiary amines product.This is owing to contain more metal ion in the higher and product of vegetable oil polyol activity, if adopt metallic catalyst can shorten the gel time of foam, influences its flowability.The consumption that wherein increases foam stabiliser is to make its mixing more abundant for the surface tension that reduces the each component material.Wherein blowing agent vaporization back is as the source of steam bubble, and takes away the heat in the reaction.Gas enters the foam micropore and forms hole-closing structure to reduce coefficient of thermal conductivity.Low amounts of water is a chain extender, and water and isocyanide ester reaction simultaneously generates carbon dioxide, also as the gas source that foams.Wherein adding fire retardant is for making foam have anti-flammability, to reach the fire protection requirement of constructional materials.Topping of the present invention adopts metal sheets such as high-density fiber cement board, tile panel, plastic plate, plastic-aluminum alloy sheets, aluminium alloys, substitutes general cement mortar grid cloth, can gain in strength, and avoids cracking.The topping outside generally will spray one deck decorative paint (title decorative layer), and for example fluorine carbon lacquer, resin emulsion paint and other external wall add coating.Decorative layer can be sprayed on the protection outside in advance, and then makes composite plate; Also can be again by design and customer requirement spraying and decorating layer after installing on the external wall.And combined wall board another side polyurethane surface will spray the one layer of polymeric interfacial agents usually, is beneficial to bonding with body of wall.
The invention will be further described below in conjunction with embodiment.
The specific embodiment:
Embodiment 1:
On tinuous production, with the topping horizontal on conveyer belt, the topping both sides are provided with block, the top be plastic sheeting, with A, B two components in the high pressure casting machine is cast in the cavity of topping and plastic sheeting, repressed slaking moulding, take plastic sheeting off and form vegetable oil radical polyurethane composite panels, it comprises polyurethane insulation coating, polyurethane insulation coating surface recombination topping, and polyurethane insulation coating and topping are by the adhesion stress bonding of polyurethane self; Along with moving ahead of transmission system, carry out serialization production.
Described topping is high-density fiber cement board (or tile panel or plastic plate or plastic-aluminum alloy sheets or aluminium alloy plate).
Described A component is an isocyanide ester, and the B component is to be made up of following weight item:
10 parts of 40 parts of oil PPGs of vegetable oil polyol
5 parts of 15 parts of crosslinking agents of PEPA
10 parts of 3 parts of catalyzer of foam stabiliser
10 parts of 30 parts of fire retardants of blowing agent
1 part in water.More than each composition in container, stir and promptly form the B component.
The consumption of A component and B component (weight) is than being 1: 0.7～1.3 (examples 1: 0.8,1: 1,1: 1.2).
Wherein vegetable oil polyol is soybean oil polyalcohol (or in the castor oil polyhydric alcohol, rapeseed oil polyalcohol, cottonseed oil polyalcohol, palm oil polyalcohol, recovered oil polyalcohol one or more); The oil PPG is glycerine (or in the sucrose, expoxy propane PPG, sorbierite, glycerine, expoxy propane PPG, ethylenediamine PPG one or more).PEPA is phthalic anhydride (or in the diethylene glycol (DEG) PEPA, glycerine PEPA one or more).Crosslinking agent is diethylene glycol (DEG) (or in the propane diols, triethanolamine one or more).Catalyzer is the rare amine of three second (33% propylene glycol solution) (or in the dimethyl amine, triethylamine one or more).Foam stabiliser is an organic silicon surfactant.Blowing agent is fluoro trichloromethane (CFC11) (or in the fluorine dichloroethanes, pentamethylene one or more); Fire retardant is dimethyl methyl phosphonate (being called for short TCPP) or three (chloro isopropyl) phosphate (being called for short DMMP) or three (β-chloroethyl) phosphate (being called for short TCEP).
Embodiment 2:
The B component is to be made up of following weight item:
35 parts of 60 parts of oil PPGs of vegetable oil polyol
30 parts of PEPAs
1 part of 5 parts of catalyzer of foam stabiliser
15 parts of 50 parts of fire retardants of blowing agent
2 parts in water.More than each composition in container, stir and promptly form the B component.
All the other are with embodiment 1.
Embodiment 3:
The B component is to be made up of following weight item:
60 parts of 80 parts of oil PPGs of vegetable oil polyol
10 parts of crosslinking agents
5 parts of 2 parts of catalyzer of foam stabiliser
6 parts of 10 parts of fire retardants of blowing agent.More than each composition in container, stir and promptly form the B component.All the other are with embodiment 1.
Claims (10)
1. vegetable oil radical polyurethane composite panels is characterized in that: comprise polyurethane insulation coating, and polyurethane insulation coating surface recombination topping, polyurethane insulation coating and topping are by the adhesion stress bonding of polyurethane self; Above-mentioned insulation layer is to be hard bubbled by the vegetable oil based polyurethane that A, B component hybrid reaction make, and described A component is an isocyanide ester, and the B component is to be made up of following weight item:
10～60 parts of 40～80 parts of oil PPGs of vegetable oil polyol
0～10 part of 0～30 part of crosslinking agent of PEPA
0.5～10 part of 2～5 parts of catalyzer of foam stabiliser
6～15 parts of 10～50 parts of fire retardants of blowing agent
0～2 part in water;
The amount ratio of A component and B component is 1: 0.7～1.3.
2. vegetable oil radical polyurethane composite panels according to claim 1 is characterized in that: topping is high-density fiber cement board, tile panel, plastic plate, plastic-aluminum alloy sheets or aluminium alloy plate.
3. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: vegetable oil polyol is one or more in soybean oil polyalcohol, castor oil polyhydric alcohol, rapeseed oil polyalcohol, cottonseed oil polyalcohol, palm oil polyalcohol, the recovered oil polyalcohol.
4. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: the oil PPG is one or more in glycerine, sucrose, expoxy propane PPG, sorbierite, glycerine, expoxy propane PPG, the ethylenediamine PPG.
5. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: PEPA is one or more in phthalic anhydride, diethylene glycol (DEG) PEPA, the glycerine PEPA.
6. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: crosslinking agent is one or more in diethylene glycol (DEG), propane diols, the triethanolamine.
7. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: catalyzer is one or more in the rare amine of three second (33% propylene glycol solution), dimethyl amine, the triethylamine.
8. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: foam stabiliser is an organic silicon surfactant.
9. vegetable oil radical polyurethane composite panels according to claim 1 and 2 is characterized in that: blowing agent is one or more in fluoro trichloromethane, a fluorine dichloroethanes, the pentamethylene; Fire retardant is dimethyl methyl phosphonate, three (chloro isopropyl) phosphate, three (β-chloroethyl) phosphate.
10. the continuous producing method of a vegetable oil radical polyurethane composite panels; it is characterized in that: on tinuous production; with the topping horizontal on conveyer belt; the topping both sides are provided with block, and the top is a plastic sheeting, with A, B two components in the high pressure casting machine is cast in the cavity of topping and plastic sheeting; repressed slaking moulding; take plastic sheeting off and form combined wall board,, carry out serialization production along with moving ahead of transmission system.
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| CN2007100238537A CN101117822B (en) | 2007-06-22 | 2007-06-22 | Vegetable oil radical polyurethane composite panels and continuous production method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103052666A (en) * | 2010-07-22 | 2013-04-17 | 建筑研究和技术有限公司 | Sealant&adhesive using green prepolymer |
| CN103342797A (en) * | 2013-07-16 | 2013-10-09 | 山东泽辉高科涂层有限公司 | Polyurethane resin for superfine fiber synthetic leather |
| CN103554475A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of polyether polyol for coal mine reinforcing material |
| CN104015462A (en) * | 2013-11-16 | 2014-09-03 | 山东华德隆建材科技有限公司 | Continuous production process of polyurethane heat-preserving composite board of fiber cement pressure plate |
| CN104818819A (en) * | 2014-12-31 | 2015-08-05 | 万华节能科技集团股份有限公司 | Compound varnish facing integrated board and processing technology thereof |
| CN104831890A (en) * | 2014-12-31 | 2015-08-12 | 万华节能科技集团股份有限公司 | Energy-saving integrated board with inorganic synthesis finish and processing technology thereof |
| CN104961876A (en) * | 2015-06-11 | 2015-10-07 | 山东一诺威新材料有限公司 | Thermoplastic hard polyurethane foam plastic for automobile interior decoration and preparation method thereof |
| WO2017063255A1 (en) * | 2015-10-14 | 2017-04-20 | 江苏绿源新材料有限公司 | Biomass-based polyurethane spray foam plastic and method for preparation thereof |
| CN106746916A (en) * | 2016-12-23 | 2017-05-31 | 宁波工程学院 | Bio-based polyurethane composite concrete material and application method |
| CN107915821A (en) * | 2016-10-10 | 2018-04-17 | 万华化学（北京）有限公司 | A kind of polyurethane foam and its preparation method and application |
| CN108822279A (en) * | 2018-07-11 | 2018-11-16 | 刘永 | A kind of environment-friendly insulating for facade, sound insulation blown polyurethane materials and preparation method thereof |
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| DE59303978D1 (en) * | 1993-03-17 | 1996-10-31 | Sto Ag | Composite insulation system |
| CN1172199A (en) * | 1996-07-29 | 1998-02-04 | 程永存 | Light-wt. high-strength composite wall panel |
| CN1326038A (en) * | 2001-07-17 | 2001-12-12 | 张小平 | Technological flow for producing decorative and insulating composite polyurethane slabs of wall |
| CN1584254A (en) * | 2004-05-27 | 2005-02-23 | 拜耳（中国）有限公司 | Polyurethane foaming primary forming thermal insulative wallboard and manufacturing process thereof |
| CN2723563Y (en) * | 2004-06-04 | 2005-09-07 | 山东莱钢建设有限公司 | Light thermal insulation composite wall plate |
| CN100424108C (en) * | 2006-04-13 | 2008-10-08 | 上海中科合臣股份有限公司 | Preparation method of plant oil polyalcohol |
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| CN103052666A (en) * | 2010-07-22 | 2013-04-17 | 建筑研究和技术有限公司 | Sealant&adhesive using green prepolymer |
| CN103342797A (en) * | 2013-07-16 | 2013-10-09 | 山东泽辉高科涂层有限公司 | Polyurethane resin for superfine fiber synthetic leather |
| CN103554475A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of polyether polyol for coal mine reinforcing material |
| CN104015462A (en) * | 2013-11-16 | 2014-09-03 | 山东华德隆建材科技有限公司 | Continuous production process of polyurethane heat-preserving composite board of fiber cement pressure plate |
| CN104818819A (en) * | 2014-12-31 | 2015-08-05 | 万华节能科技集团股份有限公司 | Compound varnish facing integrated board and processing technology thereof |
| CN104831890A (en) * | 2014-12-31 | 2015-08-12 | 万华节能科技集团股份有限公司 | Energy-saving integrated board with inorganic synthesis finish and processing technology thereof |
| CN104961876A (en) * | 2015-06-11 | 2015-10-07 | 山东一诺威新材料有限公司 | Thermoplastic hard polyurethane foam plastic for automobile interior decoration and preparation method thereof |
| CN104961876B (en) * | 2015-06-11 | 2017-12-05 | 山东一诺威新材料有限公司 | Automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof |
| WO2017063255A1 (en) * | 2015-10-14 | 2017-04-20 | 江苏绿源新材料有限公司 | Biomass-based polyurethane spray foam plastic and method for preparation thereof |
| CN107915821A (en) * | 2016-10-10 | 2018-04-17 | 万华化学（北京）有限公司 | A kind of polyurethane foam and its preparation method and application |
| CN106746916A (en) * | 2016-12-23 | 2017-05-31 | 宁波工程学院 | Bio-based polyurethane composite concrete material and application method |
| CN108822279A (en) * | 2018-07-11 | 2018-11-16 | 刘永 | A kind of environment-friendly insulating for facade, sound insulation blown polyurethane materials and preparation method thereof |
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| CN101117822B (en) | 2010-06-09 |
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Assignee: Jiangsu Luyuan New Materials Co., Ltd. Assignor: Lin Ling Contract record no.: 2012320000801 Denomination of invention: Vegetable oil radical polyurethane composite panels and continuous production method Granted publication date: 20100609 License type: Exclusive License Open date: 20080206 Record date: 20120618 |
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Owner name: JIANGSU LUYUAN NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: LIN LING Effective date: 20140411 |
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Effective date of registration: 20140411 Address after: 226000 No. 388, city road, Nantong, Jiangsu Patentee after: Jiangsu Luyuan New Materials Co., Ltd. Address before: 226000 No. 388, city road, Nantong, Jiangsu Patentee before: Lin Ling |