CN104327232A - Polyurethane foaming white material and polyurethane composition - Google Patents
Polyurethane foaming white material and polyurethane composition Download PDFInfo
- Publication number
- CN104327232A CN104327232A CN201410706412.7A CN201410706412A CN104327232A CN 104327232 A CN104327232 A CN 104327232A CN 201410706412 A CN201410706412 A CN 201410706412A CN 104327232 A CN104327232 A CN 104327232A
- Authority
- CN
- China
- Prior art keywords
- parts
- vain
- polyurethane
- polyurethane foam
- expected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CC[N+](C)(C)CC(*)O Chemical compound CC[N+](C)(C)CC(*)O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—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
- 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
- C08J9/14—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 organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—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
- 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
- C08J9/14—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 organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane foaming white material. The polyurethane foaming white material comprises combined polyether, a foaming agent and a trimerization type catalyst, wherein the foaming agent comprises trans-1-chloro-3, 3, 3-trifluoropropene, and the trimerization type catalyst is (2-hydroxypropyl) trimethyl ammonium formate. The invention further provides a polyurethane composition. The polyurethane foaming white material has stability in storage, and after the polyurethane foaming white material is placed at room temperature for 1 month, the foaming reaction speed of the polyurethane composition and the heat conduction coefficient of foam are basically unchanged.
Description
Technical field
The present invention relates to rigid polyurethane foam field, particularly relate to a kind of polyurethane foam and expect in vain and polyurethane composition.
Background technology
The trimerization type catalyzer that hard polyaminoester is conventional is mainly three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2,4,6-phenol, this trimerization type catalyzer can accelerate the post curing of foam, improve release property, be applicable to the rigid polyurethane foam combination (hard polyurethane foams premixed systems or hard polyurethane foams foamed material) of pentamethylene foaming system and hydrogen fluorohydrocarbon (Hydrofluorocarbons, HFCs) foaming system.
For tackling the upgrading of current efficiency and European Union GWP<150 (Global Warming Potential on January 1st, 2015, global warming up trend) new legislation, anti-form-1-chloro-3, 3, 3-trifluoro propene (HFO-1233zd, commodity are called LAB) as a kind of forth generation whipping agent of novel environment friendly high-efficiency, it does not fire, boiling point 19.0 DEG C, ODP (Ozone Depletion Potential, ozone depletion potential) be zero, GWP < 7, particularly due to its low thermal conductivity, well for the whipping agent of hard polyurethane foam, it is the environmentally acceptable equivalent material as HFCs, household electric appliances have been caused extensively to study and pay close attention to.
At present, the polyurethane composition preparing hard polyurethane foam generally includes: foam black material and the white material of foaming, wherein, the black material that foams is generally organic multiple isocyanate, the white material of foaming generally includes anti-form-1-chloro-3,3,3-trifluoro propene whipping agent, above-mentioned trimerization type catalyzer and conventional combined polyether.But, anti-form-1-chloro-3,3, carbon-carbon double bond in 3-trifluoro propene molecule, easily and nucleophilic reagent three (dimethylamino-propyl) Hexahydrotriazine or three (dimethylamino methyl)-2,4,6-phenol reactant, for itself and the mixed long-term storage stability of combined polyether bring difficulty, namely polyurethane foam expects that storage stability is poor in vain.To be that instant mixing is instant use existing anti-form-1-chloro-3,3,3 ,-trifluoropropene system foaming white material use-pattern, and the foaming in pipeline and hold-up vessel is expected in vain can not long-time storage, and this brings difficulty for practical application.
Wherein, may there is following reaction in anti-form-1-chloro-3,3,3 ,-trifluoropropene and amine:
Due to the existence of above-mentioned reaction, mainly there are two shortcomings in existing foaming technique:
1, speed of response decay: adopt three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2,4, the trimerization type catalyzer such as 6-phenol, with anti-form-1-chloro-3,3,3-trifluoro propene whipping agent mixes, and the amido in this trimerization type catalyzer and this whipping agent react, the Cl of generation
-the activity of catalyzer can be reduced.Adopt three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2, 4, 6-phenol is as trimerization type catalyzer and anti-form-1-chloro-3, 3, after the mixing of 3-trifluoro propene, indoor storage is placed and is placed after 2 weeks in 1 month or 50 DEG C, cream time when using it to prepare urethane foam (from be mixed into raw material and start reaction and become the milky time), gel time (from be mixed into time of the rod of the putting into foam stretched fiber when taking out) and the sticky time (from be mixed into the foam surface tack-free time) prolongation, foamable reaction slows.
2, thermal conductivity raises gradually: adopt three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2,4, the trimerization type catalyzer such as 6-phenol, with anti-form-1-chloro-3,3,3-trifluoro propene whipping agent mixes, and indoor storage is placed and placed after 2 weeks in 1 month or 50 DEG C, polyurethane composition foams, and foam thermal conductivity raises, abscess becomes large.Reason may be that amido in this trimerization type catalyzer and this whipping agent react, and reaction may produce some fluorions, and fluorion destroys Si-O-Si key in silicone molecule, make Si-O-Si bond rupture, silicone molecule amount diminishes, and efficiency reduces, and foam may be caused time serious to collapse bubble.
Foregoing, only for auxiliary understanding technical scheme of the present invention, does not represent and admits that foregoing is prior art.
Summary of the invention
Main purpose of the present invention is to provide a kind of polyurethane foam to expect in vain, be intended to solve existing polyurethane foam expect in vain in anti-form-1-chloro-3,3,3-trifluoro propene easily with three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2,4, the trimerization type catalyst reactions such as 6-phenol, cause polyurethane foam to expect in vain steady in a long-term to store, the technical problem that the foamable reaction velocity attenuation of polyurethane composition and the thermal conductivity of foam raise.
For achieving the above object, the invention provides a kind of polyurethane foam and expect in vain, described polyurethane foam expects to comprise in vain: combined polyether, whipping agent and trimerization type catalyzer;
Described whipping agent comprises anti-form-1-chloro-3,3,3 ,-trifluoropropene, and described trimerization type catalyzer is (2-hydroxypropyl) trimethylammonium ammonium formiate.
Preferably, by weight, described polyurethane foam expects to comprise in vain: combined polyether 98.5 ~ 99.7 parts, whipping agent 10 ~ 50 parts and trimerization type catalyzer 0.3 ~ 1.5 part.
Preferably, the consumption of described trimerization type catalyzer is 0.4 ~ 1.0 part.
Preferably, the consumption of described whipping agent is 20 ~ 40 parts.
Preferably, described whipping agent also comprises at least one in pentamethylene, HFC-245fa and HFC-365mfc.
Preferably, described combined polyether comprises: Sucrose polyethers 10 ~ 50 parts, and hydroxyl value is 360 ~ 440mgKOH/g; Ortho-toluene diamine polyethers 5 ~ 30 parts, hydroxyl value is 380 ~ 440mgKOH/g; Ortho-toluene diamine and glycol ether are the admixtured polyether 5 ~ 30 parts of initiator, and hydroxyl value is 380 ~ 440mgKOH/g, and glycol ether and ortho-toluene diamine weight ratio are 1 ~ 4; Aromatic polyester polyol 0 ~ 15 part, hydroxyl value is 200 ~ 330mgKOH/g; Glycerin polyether 3 ~ 10 parts, hydroxyl value is 150 ~ 260mgKOH/g; 1 ~ 2 part, water; Silicone oil 1 ~ 5 part; And composite catalyst 1.0 ~ 2.5 parts.
In addition, for achieving the above object, the present invention also provides a kind of polyurethane composition, and by weight, described polyurethane composition comprises: organic multiple isocyanate 110 ~ 165 parts and polyurethane foam as above are expected in vain.
Preferably, described organic multiple isocyanate is poly methylene poly phenyl poly isocyanate.
Preferably, the isocyanate index of described organic multiple isocyanate is 1.00 ~ 1.10.
Preferably, the isocyanate index of described organic multiple isocyanate is 1.02 ~ 1.08.
Polyurethane foam of the present invention expects to adopt (2-hydroxypropyl) trimethylammonium ammonium formiate to replace three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2 as trimerization type catalyzer in vain, 4,6-phenol, due to (2-hydroxypropyl) trimethylammonium ammonium formiate can not with anti-form-1-chloro-3,3,3-trifluoro propene whipping agent reacts, this polyurethane foam expects to have long term storage stability in vain, room temperature places 1 month, the foamable reaction speed of polyurethane composition and the thermal conductivity of foam substantially unchanged; Adopt the hard polyaminoester being somebody's turn to do (2-hydroxypropyl) trimethylammonium ammonium formiate catalyst, improve the cementability of foam, make cementability be greater than 280kPa, and improve foam surface stomata states; Adopt the hard polyaminoester of the whipping agent anti-form-1-chloro-3,3,3 ,-trifluoropropene foaming of low gas phase thermal conductivity, its thermal conductivity is less than 17.5mw/mk, and density is less than 28.0kg/m
3, and also there is good dimensional stability.
Embodiment
Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of polyurethane foam to expect in vain, polyurethane foam expects to comprise in vain: combined polyether, whipping agent and trimerization type catalyzer; Whipping agent comprises anti-form-1-chloro-3,3,3 ,-trifluoropropene, and trimerization type catalyzer is (2-hydroxypropyl) trimethylammonium ammonium formiate.
Wherein, the molecular structural formula of above-mentioned (2-hydroxypropyl) trimethylammonium ammonium formiate is as follows:
Polyurethane foam of the present invention expects to adopt (2-hydroxypropyl) trimethylammonium ammonium formiate to replace three (dimethylamino-propyl) Hexahydrotriazines or three (dimethylamino methyls)-2 as trimerization type catalyzer in vain, 4,6-phenol, avoid (2-hydroxypropyl) trimethylammonium ammonium formiate and anti-form-1-chloro-3,3,3-trifluoro propene reacts, this polyurethane foam expects to have long term storage stability in vain, room temperature places 1 month, and the foamable reaction speed of polyurethane composition, the thermal conductivity of foaming and release property are substantially unchanged.Adopting should the hard polyaminoester of (2-hydroxypropyl) trimethylammonium ammonium formiate catalysis, and foam surface is smooth, and surface air hole is few, post curing performance and cementability good, foaming properties is excellent, and cementability is greater than 280kPa.Adopt anti-form-1-chloro-3,3,3 ,-trifluoropropene as whipping agent, its ODP is zero, harmless to ozone, is a kind of desirable environmental protection whipping agent, and the thermal conductivity of the hard polyaminoester of its foaming is less than 17.5mw/mk, and density is less than 28.0kg/m
3, and also there is good dimensional stability.
In a preferred embodiment, by weight, polyurethane foam expects to comprise in vain: combined polyether 98.5 ~ 99.7 parts, whipping agent 10 ~ 50 parts and trimerization type catalyzer 0.3 ~ 1.5 part.
In a more preferred embodiment, the consumption of trimerization type catalyzer is 0.4 ~ 1.0 part.
The catalytic effect of the consumption of the trimerization type catalyzer of the preferred embodiment is better, and foam cementability is better, and open bubble is less.
In a more preferred embodiment, the consumption of whipping agent is 20 ~ 40 parts.
In a more preferred embodiment, whipping agent also comprises at least one in pentamethylene, HFC-245fa and HFC-365mfc.
In a more preferred embodiment, combined polyether comprises: Sucrose polyethers 10 ~ 50 parts, and hydroxyl value is 360 ~ 440mgKOH/g; Ortho-toluene diamine polyethers 5 ~ 30 parts, hydroxyl value is 380 ~ 440mgKOH/g; Ortho-toluene diamine and glycol ether are the admixtured polyether 5 ~ 30 parts of initiator, and hydroxyl value is 380 ~ 440mgKOH/g, and glycol ether and ortho-toluene diamine weight ratio are 1 ~ 4; Aromatic polyester polyol 0 ~ 15 part, hydroxyl value is 200 ~ 330mgKOH/g; Glycerin polyether 3 ~ 10 parts, hydroxyl value is 150 ~ 260mgKOH/g; 1 ~ 2 part, water; Silicone oil 1 ~ 5 part; And composite catalyst (not comprising trimerization type catalyzer of the present invention) 1.0 ~ 2.5 parts, this composite catalyst is catalyzer common in combined polyether.
The present invention also provides a kind of polyurethane composition, and by weight, polyurethane composition comprises: organic multiple isocyanate 110 ~ 165 parts and polyurethane foam as above are expected in vain.
In a preferred embodiment, organic multiple isocyanate is poly methylene poly phenyl poly isocyanate.
In a preferred embodiment, the isocyanate index of organic multiple isocyanate is 1.00 ~ 1.10.
The isocyanate index of the organic multiple isocyanate of the preferred embodiment is little, and release property is good, and release property is substantially unchanged.
More select in embodiment one, the isocyanate index of organic multiple isocyanate is 1.02 ~ 1.08.
The isocyanate index of the organic multiple isocyanate of this more preferred embodiment is less, and release property is better, and release property is stablized.
Embodiment 1
According to parts by weight, mix the foaming that following component obtains in polyurethane composition and expect in vain: 99.4 parts of combined polyethers (being purchased from Ningwu chemical industry), (commodity are called 0.6 part of (2-hydroxypropyl) trimethylammonium ammonium formiate
tMR-2, is purchased from Air Products & Chemicals Inc) and 28 parts of anti-form-1-chloro-3,3,3 ,-trifluoropropenes (commodity are called LAB, are purchased from Honeywell).The black material of foaming in polyurethane composition is: 134.4 parts of poly methylene poly phenyl poly isocyanates (commodity are called PM2010, are purchased from Yantai ten thousand China).
Above-mentioned polyurethane foam is expected in vain be mixed to get polyurethane composition with the black material of foaming, this mixing comprises three kinds of situations: instant mixing, Room-temperature seal are placed mixing and Room-temperature seal after 1 month and placed mixing after 2 months, and performance test when foaming, test result is see table 1.
Embodiment 2
According to parts by weight, mix the foaming that following component obtains in polyurethane composition and expect in vain: 99.5 parts of combined polyethers (being purchased from Ningwu chemical industry), (commodity are called 0.5 part of (2-hydroxypropyl) trimethylammonium ammonium formiate
tMR-2, is purchased from Air Products & Chemicals Inc) and 35 parts of anti-form-1-chloro-3,3,3 ,-trifluoropropenes (commodity are called LAB, are purchased from Honeywell).The black material of foaming in polyurethane composition is: 137.7 parts of poly methylene poly phenyl poly isocyanates (commodity are called PM2010, are purchased from Yantai ten thousand China).
Above-mentioned polyurethane foam is expected in vain be mixed to get polyurethane composition with the black material of foaming, this mixing comprises three kinds of situations: instant mixing, Room-temperature seal are placed mixing and Room-temperature seal after 1 month and placed mixing after 2 months, and performance test when foaming, test result is see table 1.
Embodiment 3
According to parts by weight, mix the foaming that following component obtains in polyurethane composition and expect in vain: 99.2 parts of combined polyethers (being purchased from Ningwu chemical industry), (commodity are called 0.8 part of (2-hydroxypropyl) trimethylammonium ammonium formiate
tMR-2, is purchased from Air Products & Chemicals Inc) and 40 parts of anti-form-1-chloro-3,3,3 ,-trifluoropropenes (commodity are called LAB, are purchased from Honeywell).The black material of foaming in polyurethane composition is: 141.4 parts of poly methylene poly phenyl poly isocyanates (commodity are called PM2010, are purchased from Yantai ten thousand China).
Above-mentioned polyurethane foam is expected in vain be mixed to get polyurethane composition with the black material of foaming, this mixing comprises three kinds of situations: instant mixing, Room-temperature seal are placed mixing and Room-temperature seal after 1 month and placed mixing after 2 months, and performance test when foaming, test result is see table 1.
Comparative example 1
According to parts by weight, mix the foaming that following component obtains in polyurethane composition and expect in vain: 99.5 parts of combined polyethers (being purchased from Ningwu chemical industry), (commodity are called 0.5 part of three (dimethylamino-propyl) Hexahydrotriazine
pC-41, is purchased from Air Products & Chemicals Inc) and 35 parts of anti-form-1-chloro-3,3,3 ,-trifluoropropenes (commodity are called LAB, are purchased from Honeywell).The black material of foaming in polyurethane composition is: 137.7 parts of poly methylene poly phenyl poly isocyanates (commodity are called PM2010, are purchased from Yantai ten thousand China).
Above-mentioned polyurethane foam is expected in vain be mixed to get polyurethane composition with the black material of foaming, this mixing comprises three kinds of situations: instant mixing, Room-temperature seal are placed mixing and Room-temperature seal after 1 month and placed mixing after 2 months, and performance test when foaming, test result is see table 1.
Comparative example 2
According to parts by weight, mix the foaming that following component obtains in polyurethane composition to expect in vain: 99.5 parts of combined polyethers (being purchased from Ningwu chemical industry), 0.5 part of three (dimethylamino methyl)-2,4, (commodity are called DMP-30 to 6-phenol, be purchased from Air Products & Chemicals Inc) and 35 parts of anti-form-1-chloro-3,3,3-trifluoro propene (commodity are called LAB, are purchased from Honeywell).The black material of foaming in polyurethane composition is: 137.7 parts of poly methylene poly phenyl poly isocyanates (commodity are called PM2010, are purchased from Yantai ten thousand China).
Above-mentioned polyurethane foam is expected in vain be mixed to get polyurethane composition with the black material of foaming, this mixing comprises three kinds of situations: instant mixing, Room-temperature seal are placed mixing and Room-temperature seal after 1 month and placed mixing after 2 months, and performance test when foaming, test result is see table 1.
Table 1
In table 1, combined polyether comprises component (1) ~ component (8), wherein,
Component (1) is Sucrose polyethers, and hydroxyl value is 360 ~ 440mgKOH/g;
Component (2) is ortho-toluene diamine polyethers, and hydroxyl value is 380 ~ 440mgKOH/g;
Component (3) for ortho-toluene diamine and glycol ether be the admixtured polyether of initiator, hydroxyl value is 380 ~ 440mgKOH/g, and glycol ether and ortho-toluene diamine weight ratio are 1 ~ 4;
Component (4) is aromatic polyester polyol, and hydroxyl value is 200 ~ 330mgKOH/g;
Component (5) is glycerin polyether, and hydroxyl value is 150 ~ 260mgKOH/g;
Component (6) is water;
Component (7) is silicone oil;
Component (8) is composite catalyst (not comprising trimerization type catalyzer of the present invention).
The standard of the performance test carried out when preparing hard polyaminoester to embodiment and comparative example is above as follows:
Cream time: from be mixed into raw material and start reaction and become the milky time;
Gel time: from be mixed into time of the rod of the putting into foam stretched fiber when taking out;
The sticky time: from be mixed into the foam surface tack-free time;
Average core density: the mean density of the foam foamed in equal dies except exterior skin, measures according to ASTM1622-88, units/kg/m
3;
Release property: the curing performance of assess foam, after certain demoulding set time, observes foam surface state, measures Foam Expansion rate.In identical demould time, Foam Expansion rate is little of, surperficial ixoderm phenomenon, then this foam formulations release property is good.Because rate of expansion also depends on die size, the result thus obtained by different mould can not compare mutually.The mould that the present invention adopts is for being of a size of 700*500*100mm;
Bonding strength: made by inner container of icebox and be of a size of 100*40mm test specimens block, often organizes 15 pieces, is pasted onto on mould, foaming, the demoulding, after 12 hours, adopts Japanese Shimadzu AGS-J universal testing machine to test bonding force, bonding strength=bonding force/sample section area, unit K Pa.Bonding strength of the present invention is the Average Bond Strength of 15 pieces of samples;
Thermal conductivity: according to ISO12939-01/DIN 52612, adopts EKO HC-074-200 conductometer to measure under medial temperature 10 DEG C (upper plate 2 DEG C, lower plate 18 DEG C).Foam prepares latter 24 hours, from the heart cutting foam sample of molding portion, and measures these samples immediately after dicing, unit mW/mK.
Found out by upper table 1, adopt (2-hydroxypropyl) trimethylammonium ammonium formiate as trimerization type catalyzer, mixing anti-form-1-chloro-3,3,3-trifluoro propene whipping agent, after Room-temperature seal places 2 months, the cream time during foaming of this polyurethane composition, gel time and not sticky time are substantially unchanged, the i.e. basic indifference of foamable reaction speed, and the thermal conductivity of foam and the basic indifference of release property.Compared with comparative example 1,2, (2-hydroxypropyl) trimethylammonium ammonium formiate effectively can improve the stability in storage of anti-form-1-chloro-3,3,3 ,-trifluoropropene in the foaming of polyurethane composition is expected in vain, and hard polyaminoester density is less than 28.0kg/m
3, thermal conductivity is less than 17.5mw/mk, and cementability is greater than 280kPa.
These are only the preferred embodiments of the present invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a polyurethane foam is expected in vain, it is characterized in that, described polyurethane foam expects to comprise in vain: combined polyether, whipping agent and trimerization type catalyzer;
Described whipping agent comprises anti-form-1-chloro-3,3,3 ,-trifluoropropene, and described trimerization type catalyzer is (2-hydroxypropyl) trimethylammonium ammonium formiate.
2. polyurethane foam as claimed in claim 1 is expected in vain, and it is characterized in that, by weight, described polyurethane foam expects to comprise in vain: combined polyether 98.5 ~ 99.7 parts, whipping agent 10 ~ 50 parts and trimerization type catalyzer 0.3 ~ 1.5 part.
3. polyurethane foam as claimed in claim 2 is expected in vain, and it is characterized in that, the consumption of described trimerization type catalyzer is 0.4 ~ 1.0 part.
4. polyurethane foam as claimed in claim 2 is expected in vain, and it is characterized in that, the consumption of described whipping agent is 20 ~ 40 parts.
5. the polyurethane foam as described in claim 2 or 4 is expected in vain, it is characterized in that, described whipping agent also comprises at least one in pentamethylene, HFC-245fa and HFC-365mfc.
6. polyurethane foam as claimed in claim 2 is expected in vain, and it is characterized in that, described combined polyether comprises: Sucrose polyethers 10 ~ 50 parts, and hydroxyl value is 360 ~ 440mgKOH/g; Ortho-toluene diamine polyethers 5 ~ 30 parts, hydroxyl value is 380 ~ 440mgKOH/g; Ortho-toluene diamine and glycol ether are the admixtured polyether 5 ~ 30 parts of initiator, and hydroxyl value is 380 ~ 440mgKOH/g, and glycol ether and ortho-toluene diamine weight ratio are 1 ~ 4; Aromatic polyester polyol 0 ~ 15 part, hydroxyl value is 200 ~ 330mgKOH/g; Glycerin polyether 3 ~ 10 parts, hydroxyl value is 150 ~ 260mgKOH/g; 1 ~ 2 part, water; Silicone oil 1 ~ 5 part; And composite catalyst 1.0 ~ 2.5 parts.
7. a polyurethane composition, is characterized in that, by weight, described polyurethane composition comprises: organic multiple isocyanate 110 ~ 165 parts and the polyurethane foam as described in claim 2 to 6 any one are expected in vain.
8. polyurethane composition as claimed in claim 7, it is characterized in that, described organic multiple isocyanate is poly methylene poly phenyl poly isocyanate.
9. polyurethane composition as claimed in claim 7 or 8, it is characterized in that, the isocyanate index of described organic multiple isocyanate is 1.00 ~ 1.10.
10. polyurethane composition as claimed in claim 9, it is characterized in that, the isocyanate index of described organic multiple isocyanate is 1.02 ~ 1.08.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410706412.7A CN104327232A (en) | 2014-11-27 | 2014-11-27 | Polyurethane foaming white material and polyurethane composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410706412.7A CN104327232A (en) | 2014-11-27 | 2014-11-27 | Polyurethane foaming white material and polyurethane composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104327232A true CN104327232A (en) | 2015-02-04 |
Family
ID=52402044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410706412.7A Pending CN104327232A (en) | 2014-11-27 | 2014-11-27 | Polyurethane foaming white material and polyurethane composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327232A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672426A (en) * | 2015-03-24 | 2015-06-03 | 合肥华凌股份有限公司 | Polyurethane composition, polyurethane foam as well as manufacture method thereof and fridge |
| CN107033327A (en) * | 2017-05-24 | 2017-08-11 | 烟台市顺达聚氨酯有限责任公司 | A kind of freezer ground high resistance to compression polyurethane combined material and preparation method thereof |
| CN107245137A (en) * | 2017-04-14 | 2017-10-13 | 合肥华凌股份有限公司 | Refrigerator combined polyether and its production and use |
| CN107522892A (en) * | 2016-06-02 | 2017-12-29 | 山东理工大学 | Purposes of the ammonium formate as polyurethane foams |
| CN108727551A (en) * | 2017-04-19 | 2018-11-02 | 科思创德国股份有限公司 | A kind of hard polyurethane foams and the preparation method and application thereof |
| CN108864396A (en) * | 2018-07-24 | 2018-11-23 | 长虹美菱股份有限公司 | A kind of refrigerator hard polyurethane foam foaming formulation and preparation method thereof |
| CN109071752A (en) * | 2016-03-07 | 2018-12-21 | 巴斯夫欧洲公司 | Hard polyurethane foams |
| CN111349206A (en) * | 2020-04-14 | 2020-06-30 | 万华节能科技(烟台)有限公司 | High-strength polyurethane heat-insulation cushion block bi-component raw material for refrigeration house and preparation method thereof |
| CN112358600A (en) * | 2020-12-02 | 2021-02-12 | 宁波耀众模塑科技有限公司 | Polyurethane automobile sun visor material blending process |
| CN114341219A (en) * | 2019-09-04 | 2022-04-12 | 赢创运营有限公司 | Phase transfer active trimerization catalyst salts |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080004362A1 (en) * | 2004-11-02 | 2008-01-03 | Tosoch Corporation | Hydroxyalkylated Polyalkylenepolyamine Composition, Method for Producing Same and Method for Producing Polyurethane Resin Using Such Hydroxyalkylated Polyalkylenepolyamine Composition |
| CN103703042A (en) * | 2011-06-08 | 2014-04-02 | 霍尼韦尔国际公司 | Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same |
| CN103804711A (en) * | 2014-02-20 | 2014-05-21 | 海信容声(广东)冰箱有限公司 | Low-thermal-conductivity rigid polyurethane foam taking cyclopentane as main body and manufacturing method and applications thereof |
| CN104119490A (en) * | 2014-07-10 | 2014-10-29 | 合肥美的电冰箱有限公司 | A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material |
-
2014
- 2014-11-27 CN CN201410706412.7A patent/CN104327232A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080004362A1 (en) * | 2004-11-02 | 2008-01-03 | Tosoch Corporation | Hydroxyalkylated Polyalkylenepolyamine Composition, Method for Producing Same and Method for Producing Polyurethane Resin Using Such Hydroxyalkylated Polyalkylenepolyamine Composition |
| CN103703042A (en) * | 2011-06-08 | 2014-04-02 | 霍尼韦尔国际公司 | Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same |
| CN103804711A (en) * | 2014-02-20 | 2014-05-21 | 海信容声(广东)冰箱有限公司 | Low-thermal-conductivity rigid polyurethane foam taking cyclopentane as main body and manufacturing method and applications thereof |
| CN104119490A (en) * | 2014-07-10 | 2014-10-29 | 合肥美的电冰箱有限公司 | A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672426B (en) * | 2015-03-24 | 2018-03-16 | 合肥华凌股份有限公司 | Urethane composition, polyurethane foam and its manufacture method and refrigerator |
| CN104672426A (en) * | 2015-03-24 | 2015-06-03 | 合肥华凌股份有限公司 | Polyurethane composition, polyurethane foam as well as manufacture method thereof and fridge |
| CN109071752A (en) * | 2016-03-07 | 2018-12-21 | 巴斯夫欧洲公司 | Hard polyurethane foams |
| CN107522892B (en) * | 2016-06-02 | 2020-08-18 | 山东理工大学 | Organic amine bicarbonate salt compound and application thereof as foaming agent |
| CN107522892A (en) * | 2016-06-02 | 2017-12-29 | 山东理工大学 | Purposes of the ammonium formate as polyurethane foams |
| CN107245137A (en) * | 2017-04-14 | 2017-10-13 | 合肥华凌股份有限公司 | Refrigerator combined polyether and its production and use |
| CN108727551A (en) * | 2017-04-19 | 2018-11-02 | 科思创德国股份有限公司 | A kind of hard polyurethane foams and the preparation method and application thereof |
| CN107033327A (en) * | 2017-05-24 | 2017-08-11 | 烟台市顺达聚氨酯有限责任公司 | A kind of freezer ground high resistance to compression polyurethane combined material and preparation method thereof |
| CN107033327B (en) * | 2017-05-24 | 2020-01-21 | 烟台市顺达聚氨酯有限责任公司 | High-compression-resistance polyurethane composite material for ground of refrigeration house and preparation method thereof |
| CN108864396A (en) * | 2018-07-24 | 2018-11-23 | 长虹美菱股份有限公司 | A kind of refrigerator hard polyurethane foam foaming formulation and preparation method thereof |
| CN114341219A (en) * | 2019-09-04 | 2022-04-12 | 赢创运营有限公司 | Phase transfer active trimerization catalyst salts |
| CN111349206A (en) * | 2020-04-14 | 2020-06-30 | 万华节能科技(烟台)有限公司 | High-strength polyurethane heat-insulation cushion block bi-component raw material for refrigeration house and preparation method thereof |
| CN111349206B (en) * | 2020-04-14 | 2022-02-08 | 万华节能科技(烟台)有限公司 | High-strength polyurethane heat-insulation cushion block bi-component raw material for refrigeration house and preparation method thereof |
| CN112358600A (en) * | 2020-12-02 | 2021-02-12 | 宁波耀众模塑科技有限公司 | Polyurethane automobile sun visor material blending process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104327232A (en) | Polyurethane foaming white material and polyurethane composition | |
| CN102443134B (en) | Polyurethane rigid foam and preparation method thereof | |
| US9453115B2 (en) | Stabilization of polyurethane foam polyol premixes containing halogenated olefin blowing agents | |
| JP5504161B2 (en) | Non-silicone surfactants for polyurethane or polyisocyanurate foams containing halogenated olefins as blowing agents | |
| CN103951966B (en) | Hard polyaminoester-aerogel silicon-dioxide syntactic foam and preparation method | |
| US20180016379A1 (en) | Foams And Foamable Compositions Containing Halogenated Olefin Blowing Agents | |
| CN103665296B (en) | Low temperature is low leads polyurethane foam, feedstock composition, combined polyether and preparation method | |
| CN104628978A (en) | Composition, rigid polyurethane foam material and refrigeration equipment | |
| CN102167899B (en) | Polyurethane rigid foam combined polyether for electric water heater | |
| CN106496494B (en) | A kind of low-density, polyurethane foam of low heat conductivity and preparation method thereof | |
| CN110628073A (en) | Formula and preparation method of polyurethane rigid foam | |
| EP2718341A2 (en) | Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same | |
| CN101555312B (en) | Rigid cellular plastic with improved property and preparation method thereof | |
| CN104497254A (en) | Composition, hard polyurethane foam material and refrigerating equipment | |
| CN102167792B (en) | Mixed foaming agent-blown polyurethane rigid foam composite polyether | |
| CN108129631A (en) | Polyurethane rigid foam plastic and preparation method thereof | |
| CN104788642A (en) | Hard polyurethane foam for ultralow-temperature insulation and preparation method thereof | |
| CN104479092A (en) | Low-density all-water open-cell hard polyurethane foam and preparation method thereof | |
| CN102229697A (en) | Solar polyurethane thermal insulation material | |
| JP2013500386A (en) | Composition of HCFO-1233zd and polyol blend for use in polyurethane foam | |
| CN102766247A (en) | Rigid polyurethane/polyvinyl chloride composite foam plastic and preparation method thereof | |
| CN101125910A (en) | Hard polyurethane foam plastic and producing method thereof | |
| CN102070412B (en) | Flame-retardant polyether glycol and preparation method thereof, combined polyether and polyurethane foam | |
| CN104262670A (en) | Foaming agent composition, polyurethane foam and manufacturing method thereof | |
| CN105085865A (en) | Special high-activity environment-friendly polyurethane thermal insulation material for refrigerator and preparation method of special high-activity environment-friendly polyurethane thermal insulation material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150204 |
|
| RJ01 | Rejection of invention patent application after publication |