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CN102079803B - Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition - Google Patents

Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition Download PDF

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Publication number
CN102079803B
CN102079803B CN200910199487XA CN200910199487A CN102079803B CN 102079803 B CN102079803 B CN 102079803B CN 200910199487X A CN200910199487X A CN 200910199487XA CN 200910199487 A CN200910199487 A CN 200910199487A CN 102079803 B CN102079803 B CN 102079803B
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combined polyether
water
polyether
type combined
full
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CN102079803A (en
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李心强
董建国
周玉波
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SHANGHAI DONGDA POLYURETHANE CO Ltd
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SHANGHAI DONGDA POLYURETHANE CO Ltd
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Abstract

The invention discloses a full-water-type combined polyether and an application method thereof. The full-water-type combined polyether comprises polyether polyol SA380, polyether polyol 310, a foam stabilizer, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine and water. The invention also discloses a composition for preparing polyurethane rigid foam. The full-water-type combined polyether disclosed by the invention overcomes the defect that Freon foaming agents used in the existing combined polyether can produce irreversible pollution in the environment, and the defects of foam deformation, higher brittleness and the like when water is used as the foaming agent. The invention provides a full-water-type combined polyether which uses water as the foaming agent; and the prepared combined polyether has the advantages of favorable thermal conductivity, excellent dimensional stability, excellent flowability, excellent demoldability and high compression strength, is especially suitable to be used as a heat insulating material in the field of solar water heaters, and has obvious environmental-protection advantage and social benefit.

Description

A kind of complete water type combined polyether and method of use, the hard polyurethane foam compsn
Technical field
The present invention relates to hard polyurethane foam foaming field, relate in particular to a kind of complete water type combined polyether and method of use thereof.The invention still further relates to a kind of hard polyurethane foam compsn that contains described complete water type combined polyether.
Background technology
Hard polyurethane foam is widely used in industries such as insulation, refrigeration, building with its excellent performance, but along with the extensive expansion of its application, its negative impact to environment has been beaten alarm bell to people.The whipping agent that the polyurethane foam industry adopts mainly contains: HCFC (HCFC), HFC (hydrogen fluorohydrocarbon), HC (alkane), liquid CO 2Or water.Whipping agent such as HCFC, HFC is all freonll-11 class (CFCs) whipping agent; The use in fluorine Lyons can consume the destruction of atmospheric ozone layer material to atmospheric ozone layer; Causing uviolizing to strengthen and threaten the existence of the mankind and other tellurians, is one of serious environmental problem the most of present face of mankind.Since 2006, the action of protection ozonosphere gets into honoured an agreement the critical period.Substitute plan according to " Montreal Agreement amendment " and national CFC, we are faced with year reduction 50% of main ODS to 2005, are cut to the challenge of zero this target to reduction 85% in 2007, by 2010.
In the CFC alternative Process; Extensively employing ODP value is zero whipping agent such as pentamethylene (or ring/iso-pentane) and transition alternate blowing agent H CFC-141B, and what China's solar water heater foaming was at present adopted is that HCFC-141B and HFC-245fa perhaps partly use HFC-365fm.These several kinds of pneumatogens all can produce Greenhouse effect to environment.
Be in environmental protection and consider, hope can be researched and developed a kind of combined polyether that can the water foaming, replaces freonll-11 class whipping agent thus.Yet, the less whipping agent that uses water as in hard polyurethane foam, major cause is: when 1. water foams, can in foam, produce CO during owing to foaming 2, normal temperature forms negative pressure down easily.Therefore need make foam solid phase intensity greater than formed negative pressure, avoid causing foam deformation.The most conventional method is that foam density is brought up to 30%, and this just causes the very big increase of cost, is difficult to promote.A kind of in addition mode recently improves foamy body through the quality that improves combined polyether and isocyanic ester, as mass ratio is brought up to 1: 1.5, causes cost to raise equally.2. water foams formed polyurethane foam because water has participated in having formed this crumbly mass of urea with the reaction of isocyanic ester, causes the shell of foam and solar water heater and inner bag not bonding.Rare complete water type combined polyether that is used for the solar water heater lagging material in the existing market.The performance index of commercially available complete water type combined polyether are:
Figure G200910199487XD00021
Summary of the invention
Technical problem to be solved by this invention is to have overcome when water is as whipping agent in the above-mentioned prior art, and the foamy body of polyurethane foam and cohesiveness reduce, and combined polyether and isocyanic ester proportioning height; The defective that causes cost to raise provides a kind of complete water type combined polyether, this combined polyether with water as whipping agent; Can take into account environmental requirement; Can solve the problem of hard polyurethane foam intensity and cohesiveness undercarriage again, and reduce the proportioning of combined polyether and isocyanic ester, cost is low.Complete water type combined polyether of the present invention is applicable to the preparation polyurethane heat insulation material, especially is suitable for the sun power polyurethane insulation coating.
For can water as whipping agent; Must avoid in foaming process, forming this crumbly mass of urea; And foamy deformation; The present invention is directed to a kind of polyether glycol for this reason, filtered out the combined polyether that can cooperate this polyether glycol use and can reach the foaming effect of excellence with excellent properties.
Therefore, the invention provides a kind of complete water type combined polyether, it comprises following each composition: polyether glycol SA380, polyether glycol 310, suds-stabilizing agent, N, N-dimethylcyclohexylamine, N, N-dimethyl benzylamine and water.
Wherein, What the mass fraction of each composition of complete water type combined polyether of the present invention was preferable is: polyether glycol SA3805-7 part, polyether glycol 3103-5 part, suds-stabilizing agent 0.2-0.3 part; N; N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
Complete water type combined polyether of the present invention is a kind of colourless to lurid transparent liquid, and its physical performance index is seen table 1.
Table 1
Figure G200910199487XD00031
Wherein, described polyether glycol SA380 is the commercially available prod, and its viscosity is 2000-3000mpa.s (25 ℃), and functionality is 6.0, and hydroxyl value is 250-350mgKOH/g, and moisture is less than 0.1%.
Wherein, described polyether glycol 310 is the conventional reagent in this area, and functionality is 3, and hydroxyl value is 100-200mgKOH/g, and moisture is less than 0.1%.
Wherein, described suds-stabilizing agent is the conventional all kinds of suds-stabilizing agents that use in hard polyurethane foam field, and preferable is siliceous class A foam A stablizer, and that better is the B8462 of goldschmidt chemical corporation and/or the L6900 of the U.S. 1 Mitugao New Material Group company 1 etc.
Wherein, N, N-dimethylcyclohexylamine and N, the N-dimethyl benzylamine is as the catalyzer of polyurethane reaction; These two kinds of catalyzer use together can be eliminated water and isocyanate reaction formation urea key and further form allophanate, and the fragility that reduces polyurethane foam also improves its cohesiveness.
What wherein, described water was preferable is deionized water.
Preferably, also can contain other conventional additives of this area in the complete water type combined polyether of the present invention as required, as long as it does not influence the technique effect of combined polyether of the present invention basically.
In the preferable instance of the present invention one; Complete water type combined polyether of the present invention is grouped into by the one-tenth of following each mass fraction: polyether glycol SA3805-7 part, polyether glycol 3103-5 part, suds-stabilizing agent 0.2-0.3 part; N; N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
Complete water type combined polyether of the present invention is mainly used in the polyurethane insulation coating of solar water heater, and than present present situation, this invention possesses tangible environment-friendly advantage and social benefit, and the shell of solar water heater is had good cohesive force.
The preparation method of complete water type combined polyether of the present invention is: each composition is pressed the mass fraction uniform mixing, promptly obtain the complete water type combined polyether.What described mixing was preferable carries out in stainless steel is puddled still, and what mixing time was preferable is 2-5 hour.
The method of use of complete water type combined polyether of the present invention can be carried out with reference to the conventional method of use of this area combined polyether.The present invention also provides a kind of method of use of described complete water type combined polyether especially, and it comprises the steps: complete water type combined polyether of the present invention and isocyanic ester (thick MDI) are pressed mass ratio 1: 1.0-1: 1.4 mixed afterreaction.Like this can be in lower scope with cost control.Under the prerequisite of not considering cost factor, the mass ratio of combined polyether of the present invention and isocyanic ester also can be higher than 1: 1.4, as with prior art in identical 1: 1.5.
The present invention also provides a kind of compsn that is used to prepare polyurethane foam, and it comprises complete water type combined polyether of the present invention and isocyanic ester, and wherein the mass ratio of combined polyether and isocyanic ester is 1: 1-1: 1.4.
Among the present invention, above-mentioned each optimum condition, can be on the basis that meets this area general knowledge arbitrary combination, promptly get each preferred embodiments of the present invention.
The reagent that the present invention uses and raw material is all commercially available gets.
Positive progressive effect of the present invention is:
1, in the complete water type combined polyether of the present invention with water as whipping agent, possessed good thermal conductivity, excellent size stability, flowability and demolding performace with the polyurethane foam that obtains after the isocyanic ester effect, compressive strength is high.
2, complete water type combined polyether of the present invention is with its good adhesive property, and the thermal insulation layer field at solar water heater has tangible environment-friendly advantage and social benefit.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
The polyether glycol SA380 that uses among the following embodiment purchases in Shanghai Dongda Polyurethane Co., Ltd
B8462 purchases in goldschmidt chemical corporation.L6900 purchases the Mitugao New Material Group company in the U.S..
Embodiment 1
The prescription of complete water type combined polyether:
Polyether glycol SA3806 part, 3104 parts of polyether glycols, silicone suds-stabilizing agent B84620.2 part, N, 0.2 part of N-dimethylcyclohexylamine, N, 0.1 part of N-dimethyl benzylamine, 0.4 part in water.
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly gets.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.2 can get foam density 35kg/m 3Sun power use polyurethane foam heat insulation material.
Embodiment 2
Complete water type combined polyether prescription:
Polyether glycol SA3805 part, 3105 parts of polyether glycols, silicone suds-stabilizing agent B84620.25 part, N, 0.25 part of N-dimethylcyclohexylamine, N, 0.2 part of N-dimethyl benzylamine, 0.3 part in water.
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly gets.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.0 can get foam density 38kg/m 3Sun power use polyurethane foam heat insulation material.
Embodiment 3
The prescription of complete water type combined polyether:
Polyether glycol SA3807 part, 3103 parts of polyether glycols, silicone suds-stabilizing agent L69000.3 part, N, 0.3 part of N-dimethylcyclohexylamine, N, 0.2 part of N-dimethyl benzylamine, 0.45 part in water,
The preparation method of complete water type combined polyether: the prescription according to the complete water type combined polyether stirs above-mentioned each composition 2 hours with 500 rev/mins under room temperature, and blowing promptly gets.
The preparation of polyurethane foam heat insulation material: combined polyether product and isocyanic ester mass ratio are that reaction in 1: 1.2 can get foam density 37kg/m 3Sun power use polyurethane foam heat insulation material.
Effect embodiment 1 sun power is with the application of complete water type combined polyether
The combined polyether of embodiment 1 is added the POL feed liquid storage tank of foaming machine, POLYMETHYLENE POLYPHENYLISOCYANATE is added the ISO feed liquid storage tank of foaming machine; The temperature of charge of adjustment foaming machine, adjustment flow and material ratio, the foaming shot (4 kilograms) of 20 vacuum pipe solars of calculating, cast, after foaming finished, the 10min demoulding was transferred to curing chamber (30-50 ℃), slaking 12h with sun power.Room temperature was placed after 3 days, and delivery is moulded bubble and detected its foaming properties, sees table 2.
Table 2
Figure G200910199487XD00061
Visible by table 2, indexs such as the intensity of the polyurethane foam heat insulation material that makes with complete water type combined polyether of the present invention, cohesiveness, rate of closed hole, dimensional stability all have raising significantly than existing combined polyether.

Claims (4)

1. complete water type combined polyether, it is characterized in that: it comprises following each composition: polyether glycol SA380, polyether glycol 310, suds-stabilizing agent, N, N-dimethylcyclohexylamine, N, N-dimethyl benzylamine and water; The mass fraction of each composition is: polyether glycol SA380 5-7 part, polyether glycol 3103-5 part, suds-stabilizing agent 0.2-0.3 part, N, N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part; Described suds-stabilizing agent is siliceous class A foam A stablizer; Described siliceous class A foam A stablizer is B8462 and/or L6900.
2. complete water type combined polyether as claimed in claim 1; It is characterized in that: described complete water type combined polyether is grouped into by the one-tenth of following each mass fraction: polyether glycol SA380 5-7 part, polyether glycol 310 3-5 parts, suds-stabilizing agent 0.2-0.3 part; N; N-dimethylcyclohexylamine 0.1-0.3 part, N, N-dimethyl benzylamine 0.1-0.2 part and water 0.3-0.45 part.
3. the method for use of a complete water type combined polyether is characterized in that: it comprises the steps: claim 1 or 2 described complete water type combined polyethers and isocyanic ester by mass ratio 1: 1.0-1: promptly get after 1.4 the mixed.
4. compsn that is used to prepare polyurethane foam, it is characterized in that: it comprises claim 1 or 2 described complete water type combined polyether and isocyanic ester, and wherein the mass ratio of combined polyether and isocyanic ester is 1: 1-1: 1.4.
CN200910199487XA 2009-11-27 2009-11-27 Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition Expired - Fee Related CN102079803B (en)

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Publication number Priority date Publication date Assignee Title
CN102604024B (en) * 2012-02-02 2013-11-13 上海东大聚氨酯有限公司 Fluorine-free flame retardant polyurethane combined polyether and using method thereof
CN103665295B (en) * 2012-09-21 2016-04-20 上海东大聚氨酯有限公司 Combined polyether, feedstock composition, polyurethane foam and its production and use
CN102942671B (en) * 2012-12-03 2014-11-05 山东一诺威新材料有限公司 External thermal-insulation environment-friendly composite polyether for delivering high-temperature media and preparation method thereof
CN103213236A (en) * 2013-04-08 2013-07-24 南京恒能新材料有限公司 Manufacturing process of polyurethane heat-insulating plate
CN103319677B (en) * 2013-07-15 2016-02-03 广西吉顺能源科技有限公司 Solar water heater water tank polyether glycol cellular insulant
CN103897142B (en) * 2013-11-13 2017-04-12 中国寰球工程有限公司 Casting type foaming-in-site deep-cooling heat insulating material for valve
CN103772636A (en) * 2013-12-25 2014-05-07 广西超星太阳能科技有限公司 Polyurethane rigid foam composition
CN106366276A (en) * 2016-08-26 2017-02-01 江苏中圣管道工程技术有限公司 High-density rigid polyurethane foam material prefabricated heat insulating pipeline and prefabricating method
CN107814899A (en) * 2017-11-13 2018-03-20 清远市蓝林新材料有限公司 Combined polyether glycol insulation material for solar water container and preparation method thereof
CN109021206A (en) * 2018-05-22 2018-12-18 南京红宝丽聚氨酯有限公司 Low-density polyurethane continuous slab preparation method in a kind of full water
CN109776748A (en) * 2019-01-22 2019-05-21 天津爱德加科技有限公司 A kind of full hydraulic matter polyurethane foam composition polyethers of high temperature resistant, hard polyurethane foams and preparation method thereof
CN111560108B (en) * 2020-05-15 2023-04-07 上海抚佳精细化工有限公司 Full-water polyurethane rigid foam and preparation method and application thereof

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US20090099274A1 (en) * 2007-10-12 2009-04-16 Michael Van Der Puy Amine catalysts for polyurethane foams
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WO2009103420A1 (en) * 2008-02-18 2009-08-27 Preform Gmbh Sound-absorbent foam system

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