CN109422862A - Hard foamed poly urethane system and its application - Google Patents
Hard foamed poly urethane system and its application Download PDFInfo
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- CN109422862A CN109422862A CN201710740383.XA CN201710740383A CN109422862A CN 109422862 A CN109422862 A CN 109422862A CN 201710740383 A CN201710740383 A CN 201710740383A CN 109422862 A CN109422862 A CN 109422862A
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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
- C08G2110/0025—Foam properties rigid
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- 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
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of hard foamed poly urethane systems, and it includes following components: A) isocyanate-reactive component；B) organic multiple isocyanate；C) fire retardant；D) catalyst；And E) chemical foaming agent.Hard foamed poly urethane system of the invention has good mobility and plane materiel caking property and anti-flammability, is very suitable for preparing discontinuous plate, especially frozen products insulated container.
Description
Technical field
The invention belongs to polyurethane fields.More particularly, it relates to a kind of hard foamed poly urethane system and its
Using.
Background technique
Shell is generally comprised by compound polyurethane material prepared by discontinuous process and is filled in polyurethane therein
Foam, the processing technology for taking first making sheet to assemble again, flexibility ratio is high, is widely used in container, freezer, board house, pipe
The heat insulating thermal preserving boards field such as road and air-conditioning thermal insulation board.
The existing compound polyurethane material prepared by discontinuous process, is prepared by following discontinuous process: will
Prefabricated shell is placed in mold, and polyurethane resin is then injected into mold, and die closing makes polyurethane resin foam to form poly- ammonia
It is demoulded after ester foam, to obtain compound polyurethane material.Polyurethane resin is usually by isocyanate component and polyol component
Reaction is formed.
In discontinuous plate preparation process, the mobility and cementability of foam system always are technology focus.If
The mobility of foam system is bad, will appear that product foam density distributivity is poor, and foam flow end is easy to appear in production
The defects of abscess deformation, bubble.Foam system adhesive property directly influences the probability of occurrence of the bubble of foamed composite, system
The service life etc. of product.
HCFC141b is generallyd use as foaming agent in current discontinuous plate preparation process, but since ODP is (to smelly
The latent energy value of the destruction of oxygen layer) and the reason of GWP (chamber effect potential value), HCFC141b will gradually be eliminated.
A kind of method for preparing hard polyurethane foam is proposed in CN101044180A, main purpose is to improve ring
Compatibility of the pentane in compound polyethers, so as to improve the applicability of foam system.In this patent, largely high using high hydroxyl value
The polyethers that degree of functionality polyethers cooperates low hydroxyl value TDA or TMP to originate, to improve the compatibility of system and pentane.But to how changing
Into foam system actual use in bonding, bubble the problems such as do not refer to.
US5895792A discloses the hard polyurethane foam preparation method for using pentamethylene as foaming agent, in the patent
The polyethers and high functionality polyethers for having used aromatic amine to originate are compound, and main purpose is the thermal degradation temperature of raising foam, but
This patent does not refer to the mobility and cementability for how improving non-HCFC141b blowing agent system.
Fire retardant generally plays fire retardation in hard polyurethane foams, there is document report different flame retardant and fire-retardant
Influence (Comparison ofDifferent Phosphorus based Flame of the number of agent to foam flame retardant effect
Retardants in Rigid Polyurethane Foam for the Production of Insulation
Materials, Heiko Tebbe, John Sawaya, CPI 2011).But it is not referred in these reports various fire-retardant
How agent helps to promote foam adhesive effect.
Therefore, from industrial reality, a kind of hard foamed poly urethane system is needed, which has excellent mobility
And caking property, so that there is better actual production processing performance, meanwhile, the flame retardant effect of the foam system is good, meets non-
Subsequent welding, the installation of continuous composite construction need.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of hard foamed poly urethane system, which has excellent
Mobility, cementability and anti-flammability.
The technical problems to be solved by the invention are addressed by the following technical programs:
According to the first aspect of the invention, a kind of hard foamed poly urethane system is provided, it includes following components:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mgKOH/g, viscosity at 25 DEG C <
200mPa.s, content are 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, 25 DEG C
Under viscosity < 15000mPas, content be 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, 25 DEG C
Under viscosity>15000mPas and<25000mPas, content be 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, 25 DEG C
Under viscosity < 30000mPas, content be 10~35 parts by weight；
The total amount of the polyether polyol is 100 parts by weight；
B) organic multiple isocyanate, using the pure and mild moisture of polyether polyols contained in the hard foamed poly urethane system as base
Standard, isocyanate index are 1.10~1.40；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein non-halogen
Fire retardant accounts for 5~40 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, contain
Amount is 0.80~2.00 parts by weight；With
E) chemical foaming agent, content is 1.00~3.00 weight %, with A) weight of isocyanate-reactive component is
Benchmark.
According to the second aspect of the invention, a kind of hard polyurethane foam is provided, above-mentioned hard polyurethane foam is passed through
The reaction of system obtains.
According to the third aspect of the invention we, a kind of method for preparing above-mentioned hard polyurethane foams is provided comprising following
Step:
I) following components is mixed and stirred for uniformly, to obtain polyalcohol premix composition:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mgKOH/g, viscosity at 25 DEG C <
200mPa.s, content are 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, 25 DEG C
Under viscosity < 15000mPas, content be 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, 25 DEG C
Under viscosity>15000mPas and<25000mPas, content be 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, 25 DEG C
Under viscosity < 30000mPas, content be 10~35 parts by weight；
The total amount of the polyether polyol is 100 parts by weight；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein non-halogen
Fire retardant accounts for 5~40 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, contents
For 0.80~2.00 parts by weight；With
E) chemical foaming agent, content is 1.00~3.00 weight %, with A) weight of isocyanate-reactive component is
Benchmark；
Ii) following B) organic multiple isocyanate is mixed with the polyalcohol premix composition to obtain rigid poly urethanes
Foam system:
B) organic multiple isocyanate, using the pure and mild moisture of polyether polyols contained in the polyalcohol premix composition as base
Standard, isocyanate index are 1.10~1.40；
Iii) make the hard foamed poly urethane system reaction to obtain hard polyurethane foam.
According to the fourth aspect of the invention, a kind of compound polyurethane material is provided comprising shell and be filled in described
The intracorporal above-mentioned hard polyurethane foam of shell.
According to the fifth aspect of the invention, a kind of method for preparing above-mentioned compound polyurethane material is provided comprising following
Step:
I) shell for having cavity is provided；
Ii) above-mentioned hard foamed poly urethane system is supplied in the cavity of the shell；With
Iii the hard foamed poly urethane system) is made to carry out foamable reaction to obtain compound polyurethane material.
Hard foamed poly urethane system of the invention have good mobile performance, and with metal (such as iron, aluminium etc.),
The plane materiels such as FRP, PS, ABS have good adhesive property, can reach the C grade flame-retardant standard of GB8410-2006, be very suitable to
In preparing discontinuous plate, especially frozen products insulated container.The core density of hard polyurethane foam of the invention is up to 35-70kg/
m3, foam rate of closed hole is up to 85-98%.
Specific embodiment
Implementation a specific embodiment of the invention is described below.
According to the first aspect of the invention, a kind of hard foamed poly urethane system is provided, it includes following components:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mg KOH/g, viscosity at 25 DEG C <
200mPa.s, content are 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, 25 DEG C
Under viscosity < 15000mPas, content be 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, 25 DEG C
Under viscosity>15000mPas and<25000mPas, content be 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, 25 DEG C
Under viscosity < 30000mPas, content be 10~35 parts by weight；
The total amount of the polyether polyol is 100 parts by weight；
B) organic multiple isocyanate, on the basis of polyethers and moisture contained in the hard foamed poly urethane system,
Isocyanate index is 1.10~1.40；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein non-halogen
Fire retardant accounts for 5~40 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, contain
Amount is 0.80~2.00 parts by weight；With
E) chemical foaming agent, 1.00~3.00 weight %, by A) isocyanate-reactive component weight on the basis of.
As used in this application, " polyether polyol " has definition well-known to those skilled in the art, can pass through
Known technical process preparation, for example, in the presence of a catalyst, being reacted and being made with initiator by alkylene oxide.
First polyether polyol a1 for use in the present invention) degree of functionality be 1.6-2.4, preferably hydroxyl value be 60-
140mgKOH/g, preferred content are 5~15 parts by weight.
As used in this application, unless otherwise specified, degree of functionality and hydroxyl value refer to average functionality and average hydroxyl value.
The measurement method of the known hydroxyl value of those skilled in the art, such as in Houben Weyl, Methoden der
Organischen Chemie,vol.XIV/2Makromolekulare Stoffe,p.17,Georg Thieme Verlag；
Disclosed in Stuttgart 1963, during the full content of the document is incorporated herein by reference.
In some embodiments of the present invention, the first polyether polyol is selected from 1,2-PD, 1,3-PD originates
Polyether polyol.
In a preferred embodiment, the first polyether polyol be selected from 1,2-PD starting based on propylene oxide
Polyether polyol.
Second polyether polyol a2 for use in the present invention) content of the low hydroxyl value polyethers of high functionality is preferably 30~50 weights
Measure part.
Third polyether polyol a3 for use in the present invention) content of high functionality high hydroxyl value polyethers is preferably 25~35 weights
Measure part.
In some embodiments of the invention, the polyether polyol that third polyether polyol is selected from sucrose, sorbierite originates.
It is highly preferred that second is selected from the polyether polyol based on propylene oxide of sucrose starting with third polyether polyol.
In one embodiment of the invention, the pure and mild third polyethers of first polyether polyol, the second polyether polyols
Polyalcohol is selected from the polyether polyol based on propylene oxide.
4th polyether polyol a4 for use in the present invention) it is preferably selected from diphenylmethanediamiand and/or toluenediamine
The polyether polyol of starting, degree of functionality 3.6-4.4, hydroxyl value 290-370mgKOH/g, preferred content are 15-25 weight
Part.
In one embodiment of the invention, the 4th polyether polyol be selected from diphenylmethanediamiand originate based on
The polyether polyol of propylene oxide.The degree of functionality of isocyanate-reactive composition comprising above-mentioned polyether polyol is 3.5-6,
Preferably 4.0-5.5, hydroxyl value 280-450mgKOH/g, preferably 290-350mgKOH/g.
The isocyanate-reactive component can also comprising selected from polyester polyol, polycarbonate polyol and they
Mixture polyalcohol, content be 0-30 parts by weight.
The polyester polyol is made by dicarboxylic acids or dicarboxylic acid anhydride with polyol reaction.The dicarboxylic acids,
It is preferably but not limited to, the aliphatic carboxylic acid containing 2-12 carbon atom, such as: succinic acid, malonic acid, glutaric acid, adipic acid, pungent two
Acid, azelaic acid, decanedioic acid, dodecyl carboxylic acid, maleic acid, fumaric acid, phthalic acid, isophathalic acid, to benzene two
Acid, their mixture.The dibasic acid anhydride, is preferably but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, it
Mixture.The polyalcohol, is preferably but not limited to, ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3-PD, dipropyl
Glycol, 1,3- methyl propanediol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, neopentyl glycol, 1,10- decanediol, third
Triol, trimethylolpropane, their mixture.The polyester polyol further includes the polyester polyol prepared by lactone.Institute
The polyester polyol prepared by lactone is stated, is preferably but not limited to, 6-caprolactone.
The polycarbonate polyol, is preferably but not limited to, polycarbonate glycol.The polycarbonate glycol, can
To be made by glycol and dialkyl or diaryl carbonate or phosgene reaction.The glycol, is preferably but not limited to, and 1,2- the third two
Alcohol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, diethylene glycol (DEG), metaformaldehyde glycol, their mixing
Object.The dialkyl or diaryl carbonate, is preferably but not limited to, diphenyl carbonate.
Component B) organic multiple isocyanate include organic diisocyanate, can be and become known for preparing polyurethane
Any aliphatic, alicyclic or aromatic isocyanate.
Component B) organic multiple isocyanate index be 1.10~1.40, preferably 1.15~1.30.
The index of the organic isocyanate referred in present specification refers to isocyanate index, usually with polyurethane
On the basis of the pure and mild moisture of polyether polyols contained in rigid foam systems or polyalcohol premix composition.It should be understood that
Since organic isocyanate is to moisture-sensitive, so substantially free of moisture, rigid poly urethanes bubble in organic isocyanate raw material
The pure and mild moisture of polyether polyols contained in the pure and mild moisture of polyether polyols contained in foam system and polyalcohol premix composition is real
It is identical in matter.
As the example of organic diisocyanate, it can be mentioned that have: 2,2 '-methyl diphenylene diisocyanates, 2,4-
Methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanates；Diphenyl methane two with three or more rings
Isocyanates homologue (polymeric MDI)；Hydrogenated diphenyl methane diisocyanate (HMDI), isophorone diisocyanate
(IPDI), the oligomer of isophorone diisocyanate；2,4 toluene diisocyanate (2,4-TDI), 2,6- toluene diisocyanate
Acid esters；The oligomer of tetramethylene diisocyanate, tetramethylene diisocyanate；Hexamethylene diisocyanate (HDI), six
The oligomer of methylene diisocyanate；Naphthalene diisocyanate (NDI).
In embodiments of the present invention, organic multiple isocyanate includes the isocyanic acid based on methyl diphenylene diisocyanate
Ester, especially comprising those of polymeric MDI.
The degree of functionality of the organic multiple isocyanate is preferably 1.9-3.5, particularly preferred 2.5-3.3.
The organic multiple isocyanate viscosity is preferably 100-600mPas, particularly preferred 150-300mPas.
Viscosity described in present specification measures at 25 DEG C according to DIN 53019-1-3.
The content of the organic isocyanate can be 20-60 weight %, relative to the hard foamed poly urethane system
Total weight.
Organic multiple isocyanate can also use polyisocyanate prepolymers.These polyisocyanate prepolymers can pass through
The chemical combination for making the excessive above-mentioned organic multiple isocyanate of one or more and there are at least two isocyanate-reactive groups
Object is reacted at a temperature of preferably 80 DEG C and is obtained at such as 30-100 DEG C.
The NCO content of polyisocyanate prepolymers of the present invention is preferably 20-33 weight %, particularly preferred 25-32 weight %.
It include halogen flame and non-halogen flame retardant for fire retardant of the invention.
As the halogen flame that can be used, it can be mentioned that example have: TCPP (tricresyl phosphate (2- chloropropyl) ester),
TCEP (trichloroethyl phosphate) etc..
As the non-halogen flame retardant that can be used, it can be mentioned that example have: TEP (triethyl phosphate), DMPP (propyl
Dimethyl phosphonate) etc..
Inventor has found that the composite flame-retardant agent comprising halogen flame and non-halogen flame retardant can change by numerous studies
Become foamy body, to influence the adhesive property of foam.
It can be common gel catalyst in hard polyurethane foam field for gel catalyst of the invention, it can be with
The example referred to has: dimethyl cyclohexyl amine and dimethyl benzylamine.
It can be common catalyst for trimerization in hard polyurethane foam field for catalyst for trimerization of the invention, it can be with
The example referred to has: methyl ammonium salt, ethyl ammonium salt, pungent quaternary amine, hexahydrotriazine and organic metal alkali.
It can be common kicker in hard polyurethane foam field for kicker of the invention, it can be with
The example referred to has: pentamethyl-diethylenetriamine, double-dimethyl amine benzyl ethyl ether, N, N, N ', N "-tetramethylethylenediamine, N, N,
N ', N "-tetramethyl butane diamine and 4-methyl hexamethylene diamine.
Those skilled in the art can be with isocyanide in the desired use of hard polyurethane foam according to the present invention and formula
Acid esters reactive component and the type of the content of organic isocyanate components selection used catalyst simultaneously adjust used catalyst
Amount.
Chemical foaming agent for use in the present invention can select common various chemical foaming agent in hard polyurethane foam field,
Such as water.
The content of chemical foaming agent is 1.00~3.00% weight, preferably 1.30~2.50% weight, with A) isocyanic acid
On the basis of the weight of ester reactive component.
Rigid poly urethanes foaming system of the invention can also include physical blowing agent, in an amount of from 8-25 parts by weight, with 100
On the basis of parts by weight polyether polyol.
Physical blowing agent for use in the present invention can select common various physical blowing agents in hard polyurethane foam field,
It is preferably but not limited to halogenated hydrocarbons (such as chlorodifluoronmethane, one fluomethane of dichloro, dichloro fluomethane, trichlorine fluoro first
Alkane, a fluorine dichloroethanes, 3-pentafluorobutane, pentafluoropropane, chlorotrifluoropropylene, hexafluorobutene), hydrocarbon compound (such as butane,
Pentane, pentamethylene, hexane, hexamethylene, heptane), gas (such as air, carbon dioxide, nitrogen).The physical blowing agent contains
Amount is 8~25 parts by weight, and preferably 9~20 parts by weight, the weight based on the isocyanate-reactive component is 100 parts by weight
Meter.
Can be used for preparing polyurethane foam of the invention component can also comprising other auxiliary agents commonly used in the art or
Additive, such as surfactant etc..
The surfactant, is preferably but not limited to, the ethylene oxide derivant of siloxanes.The use of the surfactant
Amount is that all polyalcohols in the reaction system for prepare polyurethane (had both included the polyalcohol as reactive component, and also included using
Make the polyalcohol used in the polyalcohol and other components of chain extender) dosage 0.01-5 weight %.
The core density of polyurethane foam according to the present invention is up to 35-70kg/m3,
Polyurethane foam rate of closed hole according to the present invention is up to 85-98%.
In the component that can be used for preparing polyurethane foam of the invention, isocyanate-reactive component A) and physical blowing
Agent component such as pentamethylene has good compatibility, to prepare with equally distributed foam.Meanwhile the polyurethane of preparation
Rigid foam also has good demolding performace and good surface quality.
According to a second aspect of the present invention, a kind of hard polyurethane foam is provided, the hard polyurethane foam is passed through
The reaction of system obtains.
According to the third aspect of the invention we, a kind of method for preparing above-mentioned hard polyurethane foams is provided comprising following
Step:
I) following components is mixed and stirred for uniformly, to obtain polyalcohol premix composition:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mgKOH/g, viscosity at 25 DEG C <
200mPa.s, content are 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, 25 DEG C
Under viscosity < 15000mPas, content be 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, 25 DEG C
Under viscosity>15000mPas and<25000mPas, content be 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, 25 DEG C
Under viscosity < 30000mPas, content be 10~35 parts by weight；
The total amount of the polyether polyol is 100 parts by weight；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein non-halogen
Fire retardant accounts for 5~40 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, contain
Amount is 0.80~2.00 parts by weight；With
F) chemical foaming agent, content is 1.00~3.00 weight %, with A) weight of isocyanate-reactive component is
Benchmark；
Ii) following B) organic multiple isocyanate is mixed with the polyalcohol premix composition to obtain rigid poly urethanes
Foam system:
B) organic multiple isocyanate, on the basis of polyethers and moisture contained in the polyalcohol premix composition,
Isocyanate index is 1.10~1.40；
Iii) make the hard foamed poly urethane system reaction to obtain hard polyurethane foam.
The types of the above components and amount with above for identical described in hard foamed poly urethane system.
The reaction of the hard foamed poly urethane system carries out in preferably 25-40 DEG C of environment usually at 0-50 DEG C.
According to the fourth aspect of the invention, a kind of compound polyurethane material is provided comprising shell and be filled in described
The intracorporal above-mentioned hard polyurethane foam of shell.
The shell can be prepared by panel materials such as metal, plastics and composite plates.
Compound polyurethane material can be selected from: container roof plate, side plate, bottom plate or door-plate；Movable plank house top plate, side plate or
Bottom plate or door-plate；Freezer shingle, side plate or bottom plate or door-plate；Air-conditioning thermal insulation board；Utilidor.
According to the fifth aspect of the invention, a kind of method for preparing above-mentioned compound polyurethane material is provided comprising following
Step:
I) shell for having cavity is provided；
Ii) above-mentioned hard foamed poly urethane system is supplied in the cavity of the shell；With
Iii hard foamed poly urethane system) is made to carry out foamable reaction to obtain compound polyurethane material.
The temperature of usual shell is maintained at 28~40 DEG C, and the temperature of hard foamed poly urethane system raw material is 18~25 DEG C.
The method that the present invention prepares compound polyurethane material is discrete method.
In some embodiments of the present invention, the cavity has plate or hollow cylindrical shape.
In some embodiments of the present invention, it is first prefabricated into using panel materials such as metal, plastics and composite plates first
Then shells is sealed processing to shells seam areas, and retains material hole and gas vent, shells is finally placed into foaming
In molding die, above-mentioned hard foamed poly urethane system is injected in the cavity of shells by mold and the material hole of shells,
After the completion of the foamable reaction of hard foamed poly urethane system, polyurethane can be obtained after the product to have foamed is removed from the molds
Composite material.
Unless otherwise defined, all technical and scientific terms used herein have those skilled in the art of the invention
Normally understood identical meaning.When the definition of term in this specification and the normally understood meaning of those skilled in the art of the invention
When justice is contradictory, it is subject to definition described herein.
The present invention is illustrated by the following examples, it should be understood that the scope of the present invention is not implemented by these
The restriction of example.
Embodiment
Raw materials used explanation in embodiment:
Two degree of functionality polyethers:
GR210: polyether polyol is purchased from Gaoqiao Petrochemical Company Co., Ltd, hydroxyl value: 100, viscosity: and 160mPas, degree of functionality:
2.0；
The low hydroxyl value polyethers of high functionality:
Desmophen 4030M: polyether polyol creates polymer Co., Ltd purchased from Cohan, hydroxyl value: 380, viscosity:
11250mPas, degree of functionality: 5.8；
GR8231: polyether polyol is purchased from Gaoqiao Petrochemical Company Co., Ltd, hydroxyl value: 310, viscosity: 1200mPas, function
Degree: 4.3；
High functionality high hydroxyl value polyethers:
NJ4502: polyether polyol is purchased from Jurong Ningwu New Materials Development Co., Ltd., hydroxyl value: 450, viscosity:
17000mPas, degree of functionality: 5.2；
NJ6207: polyether polyol is purchased from Jurong Ningwu New Materials Development Co., Ltd., hydroxyl value: 460, viscosity:
16000mPas, degree of functionality 5.3；
Aromatic amine starting polyether:
Z450: polyether polyol creates Taiwan Co., Ltd purchased from Cohan, hydroxyl value: 345, viscosity: 12000mPas, function
Degree: 4.0；
Fire retardant:
TCPP: halogen flame is purchased from Jiangsu Yoke Technology Co., Ltd.；
TEP: non-halogen flame retardant is purchased from Jiangsu Yoke Technology Co., Ltd.；
Surfactant:
L6920: purchased from figure new high-tech material (China) Co., Ltd advanced in years；
Foaming agent:
Pentamethylene: it is purchased from Guangzhou Mei Long company；
HFC 245fa: it is purchased from Honeywell company；
LBA: it is purchased from Honeywell company；
Catalyst:
Dabco Polycat 41 (is abbreviated as pc 41): polyurethane catalyst for trimerization, is purchased from air chemical products (China)
Co., Ltd；
Dabco polycat 8 (is abbreviated as pc 8): polyurethane gle catalyst, has purchased from air chemical products (China)
Limit company；
Dabco polycat 5 (is abbreviated as pc 5): polyurethane foaming catalyst, has purchased from air chemical products (China)
Limit company；
Organic multiple isocyanate:
44v20L:NCO content is 31.5 weight %, creates polymer (China) Co., Ltd purchased from Cohan.
Used test method illustrates in embodiment:
Fluidity testing: with the mobility of HSR flow duct test foam system, higher, the body of the final height of foam in experiment
It is that mobility is better.
Caking property test: the steel plate (50*50mm) for being coated with epoxy-based lacquers is bonded on mold, is foamed, to foam-formed
After take out, along steel plate edge cut, then by GB9641 test foam and plane materiel adhesion strength.
Compressive strength test: GB8813 standard testing is pressed.
Determination of conductive coefficients: it is tested by GB3399.
Flame retardant property test: GB8410 standard testing is pressed.
Embodiment 1-7 and comparative example 1-7
White material component is mixed by premixing device according to formula shown in table 1, machine is then premixed by high pressure
White material component is mixed with physical blowing agent, finally passes through high pressure with organic multiple isocyanate (Desmodur44V20L) again
Machine carries out die closing mixed perfusion, after reaching demoulding time (about 30 minutes), can be opened and take out the good discontinuous system of foaming
Product.
Before being irrigated, shells is first prefabricated into using steel plate, forms plate shape cavity, then to shells seam areas into
Row encapsulation process, and retain material hole and gas vent, finally shells is placed into foaming molding mold, rigid poly urethanes are steeped
Foam system is applied in the cavity of shells by the material hole of mold and shells, in the foamable reaction of hard foamed poly urethane system
After the completion, discontinuous product can be obtained after the product to have foamed being removed from the molds.
Table 1
As can be seen from Table 1, the foam system of embodiment 1 is in mobility, adhesive property, foamy body and heating conduction
General performance is best.
Table 2
From table 2 it can be seen that the formula of embodiment 4 is in foam system adhesive property in the type selecting proportion of different flame retardant
And it puts up the best performance in terms of other comprehensive performances.
Table 3
From table 3 it is observed that hard polyurethane foam of the invention tie up to it is excellent in terms of foam adhesive property.
Pass through the comparison to different foaming agents, it can be seen that in different blowing agent systems, halogen flame and non-halogen
Flame retardant combination uses the adhesion strength that can effectively improve foam system.
Although the present invention is described in detail above with respect to the object of the invention, it will be appreciated that, this detailed description is
Illustratively, other than the content that can be defined by the claims, without departing from spirit and scope of the present invention,
Those skilled in the art can carry out various changes.
Claims (10)
1. a kind of hard foamed poly urethane system, which is characterized in that it includes following components:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mgKOH/g, viscosity < 200mPa.s at 25 DEG C contain
Amount is 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, at 25 DEG C
Viscosity < 15000mPas, content are 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, at 25 DEG C
Viscosity>15000mPas and<25000mPas, content are 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, at 25 DEG C
Viscosity < 30000mPas, content are 10~35 parts by weight；
The total amount of the polyether polyol is 100 parts by weight；
B) organic multiple isocyanate, on the basis of polyether polyol and moisture contained in the hard foamed poly urethane system,
Its isocyanate index is 1.10~1.40；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein halogen-free flame-retardant
Agent accounts for 5~50 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, content is
0.80~2.00 parts by weight；With
E) chemical foaming agent, content is 1.00~3.00 weight %, by A) on the basis of the weight of isocyanate-reactive component.
2. hard foamed poly urethane system according to claim 1, which is characterized in that the organic multiple isocyanate is choosing
From one or more of components below: 2,2 '-methyl diphenylene diisocyanates, 2,4- methyl diphenylene diisocyanate,
4,4 '-methyl diphenylene diisocyanates；Methyl diphenylene diisocyanate homologue (polymerization with three or more rings
MDI)；Hydrogenated diphenyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI), isophorone diisocyanate
The oligomer of ester；2,4- toluene di-isocyanate(TDI)s (2,4-TDI), 2,6- toluene di-isocyanate(TDI)s；Tetramethylene diisocyanate,
The oligomer of tetramethylene diisocyanate；Hexamethylene diisocyanate (HDI), hexamethylene diisocyanate it is oligomeric
Object；Naphthalene diisocyanate (NDI)；And above-mentioned organic multiple isocyanate with at least two isocyanate-reactive groups
The obtained compound of compound.
3. hard foamed poly urethane system according to claim 1 or 2, which is characterized in that first polyether polyol,
The pure and mild third polyether polyol of second polyether polyols is selected from the polyether polyol based on propylene oxide.
4. hard foamed poly urethane system according to claim 1 or 2, which is characterized in that the isocyanate-reactive
Component also includes one or more of polyalcohols selected from polyester polyol, polycarbonate polyol and their mixture.
5. a kind of hard polyurethane foam, which is characterized in that it passes through rigid poly urethanes of any of claims 1-4
The reaction of foam system obtains.
6. a kind of method for preparing hard polyurethane foams described in claim 5, which is characterized in that itself the following steps are included:
I) following components is mixed and stirred for uniformly, to obtain polyalcohol premix composition:
A) isocyanate-reactive component, the isocyanate-reactive component include following polyether polyol:
A1) the first polyether polyol: two degree of functionality polyethers, hydroxyl value < 200mgKOH/g, viscosity < 200mPa.s at 25 DEG C contain
Amount is 5~20 parts by weight；
A2) the second polyether polyol: the low hydroxyl value polyethers of high functionality, degree of functionality>4, hydroxyl value<400mgKOH/g, at 25 DEG C
Viscosity < 15000mPas, content are 15~65 parts by weight；
A3) third polyether polyol: high functionality high hydroxyl value polyethers, degree of functionality > 4, hydroxyl value > 400mgKOH/g, at 25 DEG C
Viscosity>15000mPas and<25000mPas, content are 10~40 parts by weight；
A4) the 4th polyether polyol: aromatic amine starting polyether, degree of functionality < 4.5, hydroxyl value < 400mgKOH/g, at 25 DEG C
Viscosity < 30000mPas, content are 10~35 parts by weight；
The polyether polyol total amount is 100 parts by weight；
C) fire retardant, it includes halogen flame and non-halogen flame retardant, content is 5~25 parts by weight, wherein halogen-free flame-retardant
Agent accounts for 5~40 weight % of whole fire retardants；
D) catalyst, it includes one of kicker, gel catalyst and catalyst for trimerization or more, content is
0.80~2.00 parts by weight；With
E) chemical foaming agent, content is 1.00~3.00 weight %, by A) on the basis of the weight of isocyanate-reactive component；
Ii) following B) organic multiple isocyanate is mixed with the polyalcohol premix composition to obtain hard polyurethane foam
System:
B) organic multiple isocyanate, on the basis of the pure and mild moisture of polyether polyols contained in the polyalcohol premix composition,
Its isocyanate index is 1.10~1.40；
Iii) make the hard foamed poly urethane system reaction to obtain hard polyurethane foam.
7. a kind of compound polyurethane material, which is characterized in that it includes shell and to be filled in the shell intracorporal according to right
It is required that hard polyurethane foam described in 5.
8. compound polyurethane material according to claim 7, which is characterized in that the shell by selected from metal, plastics and
The panel material of composite plate is prepared.
9. compound polyurethane material according to claim 7, which is characterized in that the compound polyurethane material is selected from: collection
Vanning top plate, side plate, bottom plate or door-plate；Movable plank house top plate, side plate or bottom plate or door-plate；Freezer shingle, side plate or bottom plate
Or door-plate；Air-conditioning thermal insulation board；Utilidor.
10. a kind of method for preparing compound polyurethane material described in any one of claim 7-9, which is characterized in that it is wrapped
Include following steps:
I) shell for having cavity is provided；
Ii) hard foamed poly urethane system of any of claims 1-4 is supplied in the cavity of the shell；With
Iii the hard foamed poly urethane system) is made to carry out foamable reaction to obtain compound polyurethane material.
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| CN201710740383.XA CN109422862B (en) | 2017-08-25 | 2017-08-25 | Rigid polyurethane foam systems and their use |
| PCT/EP2018/072568 WO2019038289A1 (en) | 2017-08-25 | 2018-08-21 | Rigid polyurethane foam system and application thereof |
| EP18756244.2A EP3672999A1 (en) | 2017-08-25 | 2018-08-21 | Rigid polyurethane foam system and application thereof |
| US16/640,773 US20210032398A1 (en) | 2017-08-25 | 2018-08-21 | Rigid polyurethane foam system and application thereof |
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| CN115135686A (en) * | 2020-02-17 | 2022-09-30 | 陶氏环球技术有限责任公司 | Rigid polyurethane foams |
| CN117126361A (en) * | 2023-09-01 | 2023-11-28 | 江苏中圣管道工程技术有限公司 | Multi-system glass fiber reinforced flame-retardant low-temperature polyurethane foam material and preparation method thereof |
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| CN117126361A (en) * | 2023-09-01 | 2023-11-28 | 江苏中圣管道工程技术有限公司 | Multi-system glass fiber reinforced flame-retardant low-temperature polyurethane foam material and preparation method thereof |
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