CN103694438B - A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof Download PDFInfo
- Publication number
- CN103694438B CN103694438B CN201310669741.4A CN201310669741A CN103694438B CN 103694438 B CN103694438 B CN 103694438B CN 201310669741 A CN201310669741 A CN 201310669741A CN 103694438 B CN103694438 B CN 103694438B
- Authority
- CN
- China
- Prior art keywords
- halogen
- urethane foam
- free flame
- rigid urethane
- composite
- 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.)
- Active
Links
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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
-
- 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
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- 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
-
- 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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
-
- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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
Abstract
The invention discloses a kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof, by composition weight number, urethane foam is made up of polyol blends 100 parts, polyisocyanates 105 ~ 180 parts, composite halogen-free flame retardants 20 ~ 80 parts, whipping agent 1 ~ 50 part, composite catalyst 1 ~ 3 part, suds-stabilizing agent 2 ~ 4 parts and linking agent 1 ~ 2 part.The product that the present invention obtains has high flame retardant, and the raw material of use is not halogen-containing, and burning can not produce the toxic gases such as hydrogen halide, has the feature of environmental protection; The raw material used is easy to get, with low cost, thus greatly reduces the manufacturing cost of urethane foam of the present invention; Urethane foam of the present invention also has the feature had wide range of applications, and is applicable to the cold-storage insulation industries such as building exterior wall heat preserving, piping insulation and refrigerator.
Description
Technical field
The present invention relates to a kind of urethane foam, particularly relate to a kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof; Belong to technical field of polymer materials.
Background technology
Rigid urethane foam is a kind of heat-insulating material and structured material of excellent property, and its great advantage is that light weight, heat-insulation and heat-preservation are good, strong with other materials cohesiveness, has higher compressive strength and good dimensional stability.Therefore, rigid urethane foam receives to be paid attention to widely and develops rapidly, and it partly can replace timber, metal and other plastics, and range of application almost penetrates into national economy every field, has become one of indispensable macromolecular material.
Although urethane foam has plurality of advantages, but its poor fire, product very easily burns and causes fire failure to grow prosperity, so not only can cause huge financial loss, even also loss of life and personal injury can be caused, non-flame resistant urethane foam serves as repeatedly takes life killer by force, and people ignorant of the fact tremble with fear to urethane foam.
The fire-retardant of current urethane foam is mainly divided into two kinds, a kind of is by adding the fire retardant material of fire retardant, additive flame retardant is as phosphoric acid ester, halogenated phosphate, clorafin, aluminium hydroxide etc., along with the increase of addition can improve flame retardant effect as far as possible, but the physical and mechanical properties of material significantly declines, and along with adding the prolongation of time, can there is migration and make Flame Retardancy decline in the liquid flame retardant in material.After traditional Halogen phosphate flame retardant spins off from polymeric system, not easily degrade and tremendous influence is caused to environment, discharging hydrogen halide in combustion and there is pungency, corrodibility, the security of the lives and property of serious threat people.Another kind is the reaction-type flame-retarding material containing flame retarding construction in molecular structure, reaction-type flame-retarding is imported at the same time or separately in polyol structure by chemical reaction the structures such as ignition-proof element phosphorus, halogen, nitrogen or phenyl ring, and make polyurethane foamed material have flame retardant properties.Reactive flame retardant participates in reaction as a kind of reacted constituent, and little on material property impact, flame retarding construction is stably attached in polyurethane macromolecular matrix, makes urethane itself containing flame-retardant composition, can not separate out in life-time service process and reduce flame retardant effect.But the complex manufacturing of reaction-type flame-retarding polyvalent alcohol, synthesis cycle is long, and cost is high, not extensive in actual applications.
Summary of the invention
The object of the invention is to propose a kind of halogen-free flame-retardant rigid urethane foam, this porous plastics, while ensure that excellent physical and mechanical property and thermal and insulating performance, also has the features such as high flame retardant, with low cost and halogen-free environmental.
In order to solve prior art problem, the present invention is achieved by the following technical solutions.
A kind of halogen-free flame-retardant rigid urethane foam: in mass fraction, its composition of raw materials is: polyol blends 100 parts, polyisocyanates 105 ~ 180 parts, composite halogen-free flame retardants 20 ~ 80 parts, whipping agent 1 ~ 50 part, composite catalyst 1 ~ 3 part, suds-stabilizing agent 2 ~ 4 parts and linking agent 1 ~ 2 part;
The molecular-weight average of described polyol blends is 200 ~ 600g/mol, hydroxyl value is 300 ~ 800mgKOH/g, the viscosity of temperature 25 DEG C time is 2000 ~ 6000MPas;
Described composite halogen-free flame retardants is 1:(0.5 ~ 1.5 by weight ratio) phosphate ester flame retardants and urea is composite forms;
Described whipping agent is butane, pentamethylene, Skellysolve A, iso-pentane, 1,1,1,2 ?Tetrafluoroethane, 1,1,1,3,3 ?pentafluoropropane, 1,1,1,3,3 ?one or more in 3-pentafluorobutane and water;
Described composite catalyst is be (1.5 ~ 3) by mass ratio: the tertiary amine catalyst of 1 and organometallic compound composite and obtain;
Described suds-stabilizing agent is type siloxane suds-stabilizing agent;
Described linking agent is glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6 ?any one or more in dihydroxyhexane, trolamine, tri-isopropanolamine, tetramethylolmethane and polyether-tribasic alcohol.
Further, described polyvalent alcohol be in polyether glycol and polyester polyol one or more.
Described polyisocyanates is any one in a kind of in diphenylmethanediisocyanate and polymethylene multi-phenenyl isocyanate or their modifier.
Described phosphate ester flame retardants is any one or more in dimethyl methyl phosphonate, diethyl ethylphosphate, propyl group dimethyl phosphate, ISOPROPYL PHENYL DIPHENYL PHOSPHATE, triethyl phosphate, tricresyl phosphate (butoxyethyl group) ester, triphenylphosphate, Tritolyl Phosphate, Resorcinol two (diphenyl phosphoester) and low polyphosphate.
Described tertiary amine catalyst is triethylamine, triethylene diamine, N, N ?diethylethanolamine, N, N ?dimethylethanolamine, dimethylaminoethoxyethanol, trolamine, trimethyl hydroxyethylammonium propylene diamine, trimethyl hydroxyethylammonium quadrol, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohol, tri-isopropyl amine, tri-isopropanolamine, Tributylamine, two (dimethylaminoethyl) ether, N, N ?dimethylcyclohexylamine, five methyl diethylentriamine, Tetramethyl Ethylene Diamine, 4-methyl hexamethylene diamine, 2, 4, 6 ?three (dimethylamino methyl) phenol, 1, 3, 5 ?three (dimethylamino-propyl) Hexahydrotriazine, N ?ethyl morpholine, N ?methylpiperazine, N ?crassitude, N ?picoline, N ?Methylimidazole, N, N ?any one or more in dimethyl benzylamine and three (dimethylamino-propyl) amine.
Described organometallic compound is any one or more in dibutyl tin laurate, stannous octoate, tin acetate, dibutyltin diacetate, dioctyl tin diacetate, two (dodecyl sulphur) dibutyl tin, isocaprylic acid potassium, Potassium ethanoate and potassium oleate.
The preparation method of described halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyol blends, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, mix and obtain A material;
(2) polyisocyanates and described A are expected control temperature is 20 ~ 35 DEG C respectively, in the environment of 20 ~ 35 DEG C, polyisocyanates is added in A material, then material is stirred, then pour in mould and carry out foaming and the demoulding;
(3) foam of depanning carries out post curing treatment, the curing temperature 80 ~ 100 DEG C of post curing, curing time 4 ~ 12h.
The temperature of described foaming is preferably 25 ~ 30 DEG C, relative humidity is preferably 25 ~ 60%.
The speed of step (2) described stirring is preferably 3000 ~ 4500r/min, the time of stirring is preferably 10 ~ 20s.
In the present invention, polyol blends and mentioned whipping agent have good consistency and mobility, and both can well be together compatible, also can ensure thermal and insulating performance and the dimensional stability of urethane foam simultaneously.Polyvalent alcohol be selected from polyether glycol and polyester polyol one or more, preferred molecular-weight average is 200 ~ 600g/mol, hydroxyl value is 300 ~ 800mgKOH/g, the viscosity of temperature 25 DEG C time is the polyol blends of 2000 ~ 6000MPas, more preferably hydroxyl value is 350 ~ 700mgKOH/g, the viscosity of temperature 25 DEG C time is the polyol blends of 2000 ~ 5000MPas, most preferably hydroxyl value is 400 ~ 600mgKOH/g, the viscosity of temperature 25 DEG C time is the polyol blends of 2000 ~ 4000MPas, specifically can by polyethers 4110, polyethers 4110H, polyethers 835, polyethers 888, polyethers 403, polyethers 210, in Polyether 220 and polyethers 330, any two kinds are mixed to get.
In the present invention, polyisocyanates refers to that functional group's degree is the polymethylene multi-phenenyl isocyanate of 2 ~ 5, be more preferably the polymethylene multi-phenenyl isocyanate that functional group's degree is 3 ~ 4, be specially any one in tolylene diisocyanate, diphenylmethanediisocyanate, polymethylene multi-phenenyl isocyanate or their modifier.Mentioned polyisocyanates has good bubble mobility energy and post curing performance, can better allow the reaction of each component be tending towards complete, thus improves the physical and mechanical property of urethane foam.
The present invention adopts by phosphate ester flame retardants and the composite composite halogen-free flame retardants of urea, and the weight ratio of phosphate ester flame retardants and urea is 1:(0.5 ~ 1.5), preferable quality is than 1:(0.7 ~ 1.3), be better 1:(0.8 ~ 1.2).Small by the physical and mechanical property impact of the composite compound flame retardant obtained on urethane foam, almost do not have, thus ensure that urethane foam has good physical and mechanical property; In the present invention, urea can regard reactive flame retardant and small molecule chain extender as, effectively can ensure the thermal and insulating performance of urethane foam, and can further improve the physicals of urethane foam; In addition, phosphate ester flame retardants and urea have good cooperative flame retardant effect, make the oxygen index of obtained urethane foam arrive about 30.The above-mentioned phosphate ester flame retardants mentioned is selected from dimethyl methyl phosphonate, diethyl ethylphosphate, propyl group dimethyl phosphate, ISOPROPYL PHENYL DIPHENYL PHOSPHATE, triethyl phosphate, tricresyl phosphate (butoxyethyl group) ester, triphenylphosphate, Tritolyl Phosphate, Resorcinol two (diphenyl phosphoester) and low polyphosphate, role is similar in the present invention for the above-mentioned material mentioned, can mutually replace using, and can be a kind of composite with urea separately, also optional wherein several carry out composite use.
In the present invention, the material mentioned by whipping agent can a kind ofly separately use, also optional wherein several used in combination, and when selecting water and other materials are used in combination, foaming effect better, is more preferably water and is used alone.Selected whipping agent has lower boiling point and higher vapour pressure, also urethane foam performance under cryogenic can be improved, when several combinationally using, urethane foam has larger mechanical property in certain temperature range, and can further improve the heat conductivility of plastics.
When water is used alone, with the metering of the polyol blends of 100 parts by weight, water usage quantity is 1 ~ 10 part, is 2 ~ 8 parts preferably, is better 3 ~ 5 parts.
When water and pentamethylene, Skellysolve A are or/and when iso-pentane is used in combination, the usage quantity selection range of water is as identical when water is used alone, pentamethylene, Skellysolve A, or/and the usage quantity of iso-pentane is relative to the polyol blends of 100 parts by weight, are 10 ~ 30 parts preferably.
When water and 1,1,1,3,3 ?pentafluoropropane, 1,1,1,3,3 ?3-pentafluorobutane time, the usage quantity of water is preferably 1 ~ 5 relative to the polyol blends of 100 mass parts, and 1,1,1,3,3 ?pentafluoropropane, 1,1,1,3,3 ?the usage quantity of 3-pentafluorobutane relative to the polyol blends of 100 mass parts, be preferably 20 ~ 50 parts.
In the present invention, composite catalyst by tertiary amine catalyst and organometallic compound composite and obtain, the mass ratio of tertiary amine catalyst and organometallic compound is (1.5 ~ 3): 1, composite catalyst can well promote amine esterification, high catalytic activity and selectivity is had to foaming process, there is stronger foaming effect simultaneously, the mobility of foam can be improved, be conducive to the preparation of urethane foam.Tertiary amine catalyst is triethylamine, triethylene diamine, N, N ?diethylethanolamine, N, N ?dimethylethanolamine, dimethylaminoethoxyethanol, trolamine, trimethyl hydroxyethylammonium propylene diamine, trimethyl hydroxyethylammonium quadrol, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohol, tri-isopropyl amine, tri-isopropanolamine, Tributylamine, two (dimethylaminoethyl) ether, N, N ?dimethylcyclohexylamine, five methyl diethylentriamine, Tetramethyl Ethylene Diamine, 4-methyl hexamethylene diamine, 2, 4, 6 ?three (dimethylamino methyl) phenol, 1, 3, 5 ?three (dimethylamino-propyl) Hexahydrotriazine, N ?ethyl morpholine, N ?methylpiperazine, N ?crassitude, N ?picoline, N ?Methylimidazole, N, N ?the combination of any one or several in dimethyl benzylamine and three (dimethylamino-propyl) amine, role is similar in the present invention for the above-mentioned material mentioned, can mutually replace using, described organometallic compound is the combination of any one or several in dibutyl tin laurate, stannous octoate, tin acetate, dibutyltin diacetate, dioctyl tin diacetate, two (dodecyl sulphur) dibutyl tin, isocaprylic acid potassium, Potassium ethanoate and potassium oleate, role is similar in the present invention for the above-mentioned material mentioned, can mutually replace using.
In the present invention, suds-stabilizing agent is type siloxane suds-stabilizing agent, be preferably Si ?the silane suds-stabilizing agent of C type, there is no particular determination, the surface tension of urethane raw mixture can be reduced, be raised up between the maturation period at foam, the material preventing the thermodynamics unstable state of foam from occurring by surface tension all can be selected.In order to give product heat-proof quality, specifically can be selected from any one or several combinations in AK8801, AK8802, AK8803, AK8805, AK8809, AK8811, AK8812, AK8832 and AK8868, the suds-stabilizing agent of described model is bought by Nanjing Dymatic Shichuang Chemical Co., Ltd. and is obtained.
In the present invention, the present invention has linking agent to select glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6 ?the combination of any one or several in dihydroxyhexane, trolamine, tri-isopropanolamine, tetramethylolmethane and polyether-tribasic alcohol, the interpolation of linking agent improves the cross-linking density of foam effectively in addition, prevent the cracking of foam in urethane foam preparation process, also improve the hardness of urethane foam simultaneously.
The each parameter controlled in the preparation method of urethane foam of the present invention is difference according to components by weight and through test of many times gained, the selection of parameter is applicable to the performance of urethane foam of the present invention.
Relative to prior art, tool of the present invention has the following advantages:
1) the present invention is undertaken composite by phosphate ester flame retardants and urea, and the physicals impact of the compound flame retardant obtained on urethane foam is small, does not almost have, thus ensure that urethane foam has good physicals; Urea can regard reactive flame retardant and small molecule chain extender as, effectively can ensure the thermal and insulating performance of urethane foam, and can further improve the physical and mechanical property of urethane foam; In addition, phosphate ester flame retardants and urea have good cooperative flame retardant effect, make the oxygen index of obtained urethane foam arrive about 30.
2) raw material used in the present invention is not halogen-containing, and burning can not produce the toxic gases such as hydrogen halide, has the feature of environmental protection.
3) raw material used is easy to get, with low cost, and product manufacture is simple, greatly reduces the manufacturing cost of urethane foam of the present invention, favourable enterprise development.
4) urethane foam of the present invention also has the feature had wide range of applications, and specifically can be building exterior wall heat preserving, the cold-storage insulation such as piping insulation, refrigerator industry.
Embodiment
For understanding the present invention better, below by way of specific embodiment, the invention will be further described, but embodiments of the present invention are not limit so.
Embodiment 1
Prepare raw material that halogen-free flame-retardant rigid urethane foam uses as following table 1:
Table 1
| Component | Material name | Parts by weight |
| Polyol blends | Polyol blends | 100 |
| Polyisocyanates | Diphenylmethanediisocyanate | 105 |
| Compound flame retardant | Compound flame retardant | 20 |
| Whipping agent | Butane | 20 |
| Composite catalyst | Composite catalyst | 1.0 |
| Suds-stabilizing agent | AK8801 | 2.0 |
| Linking agent | Glycerine | 1.0 |
In table 1, compound flame retardant is the dimethyl methyl phosphonate of 1:0.5 and urea is composite obtains by weight ratio; Polyol blends is that the polyethers 4110 of 2.5:1 and polyethers 4110H form by weight ratio, and particular case is in table 6; Composite catalyst is that the triethylene diamine solution of 1.5:1 and dibutyl tin laurate compound obtain by weight ratio, and triethylene diamine solution is the dipropylene glycol solution that triethylene diamine mass content accounts for 33%.
In the present embodiment, butane also can by pentamethylene, Skellysolve A, iso-pentane, 1,1,1,3,3 ?pentafluoropropane and 1,1,1,3,3 ?3-pentafluorobutane or 1,1,1,2 ?Tetrafluoroethane replace using.
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyether polyol mixtures, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, stir and obtain A material;
(2) diphenylmethanediisocyanate and A material are heated up, temperature controls between 20 ~ 25 DEG C, and be in the environment of 20 ~ 25 DEG C, diphenylmethanediisocyanate is added in A material in temperature, then material is stirred, stir speed (S.S.) is 3000r/min, churning time 10s, pour into again in mould carry out foaming, slaking and releasing process, wherein, foaming condition is: temperature is 25 DEG C, relative humidity is 25%;
(3) foam of depanning carries out post curing treatment, the curing temperature 80 DEG C of post curing, curing time 4h.
Embodiment 2
Prepare raw material that halogen-free flame-retardant rigid urethane foam uses as following table 2:
Table 2
| Component | Material name | Parts by weight |
| Polyol blends | Polyether polyol mixtures | 100 |
| Polyisocyanates | MR‐200 | 125 |
| Compound flame retardant | Compound flame retardant | 30 |
| Whipping agent | Water | 10 |
| Composite catalyst | Composite catalyst | 1.5 |
| Suds-stabilizing agent | AK8802 | 2.5 |
| Linking agent | TriMethylolPropane(TMP) | 1.2 |
In table 2, compound flame retardant is the triethyl phosphate of 1:0.8 and urea is composite obtains by weight ratio; Polyether polyol mixtures is that the polyethers 4110 of 1.5:1 and polyethers 4110H form by weight ratio, and particular case is in table 6; Composite catalyst is that the N of 1.5:1, N ?diethylaluminum ethoxide amine aqueous solution and stannous octoate compound obtain by weight ratio, and N, N ?diethylaluminum ethoxide amine aqueous solution is the dipropylene glycol solution that N, N ?diethylethanolamine mass content accounts for 33%.
Polymeric MDI MR ?200 fundamental propertys:
The place of production: Japanese Ruian
Isocyanate content (Wt%): 30 ?32
Viscosity (mPas/25 DEG C): 170 ?230
Hydrolyzable chloride content (Wt%) :≤0.3
Acidity (%, in HCI)≤0.05
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyether polyol mixtures, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, stir and obtain A material; Wherein composite catalyst is that the triethylene diamine of 1.5:1 and dibutyl tin laurate compound obtain by weight ratio, triethylene diamine is the dipropylene glycol solution of triethylene diamine content 33%, and compound flame retardant is the dimethyl methyl phosphonate of 1:0.5 and urea is composite obtains by weight ratio;
(2) to MR ?200 and A material heat up, temperature controls between 25 ~ 30 DEG C, and in temperature be in the environment of 25 ~ 30 DEG C by MR ?200 add in A material, then material is stirred, stir speed (S.S.) is 3500r/min, churning time 20s, pour into again in mould carry out foaming, slaking and releasing process, wherein, foaming condition is: temperature is 28 DEG C, relative humidity is 40%;
(3) foam of depanning carries out post curing treatment, the curing temperature 90 DEG C of post curing, curing time 8h.
Embodiment 3
Prepare raw material that halogen-free flame-retardant rigid urethane foam uses as following table 3:
Table 3
In table 3, compound flame retardant is the triphenylphosphate of 1:1.2 and urea is composite obtains by weight ratio; Polyether polyol mixtures is that the polyethers 4110 of 1:1 and polyethers 4110H form by weight ratio, particular case is in table 6, composite catalyst is that the triethanolamine solution of 3:1 and isocaprylic acid potassium compound obtain by weight ratio, and triethanolamine solution is the dipropylene glycol solution that trolamine mass content accounts for 33%.
MDI3051 fundamental property:
Outward appearance: colourless transparent liquid
Density (25 DEG C, g/cm3): 1.22
NCO content: 33.6%
Viscosity (25 DEG C, mPa.s): 14
Vapour pressure (25 DEG C, mmHg): <0.00001
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyether polyol mixtures, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, stir and obtain A material;
(2) MDI3051 and A material is heated up, temperature controls between 30 ~ 35 DEG C, and be in the environment of 30 ~ 35 DEG C, MDI3051 is added in A material in temperature, then material is stirred, stir speed (S.S.) is 4000r/min, churning time 20s, pour into again in mould carry out foaming, slaking and releasing process, wherein, foaming condition is: temperature is 30 DEG C, relative humidity is 60%;
(3) foam of depanning carries out post curing treatment, the curing temperature 100 DEG C of post curing, curing time 12h.
Embodiment 4
The present embodiment prepares raw material that halogen-free flame-retardant rigid urethane foam uses as following table 4:
Table 4
In table 4, compound flame retardant is the Tritolyl Phosphate of 1:1.3 and urea is composite obtains by weight ratio; Polyether polyol mixtures is that the polyethers 835 of 1:1 and polyethers 888 form by weight ratio, particular case is in table 6, composite catalyst is that the triethanolamine solution of 3:1 and tin acetate compound obtain by weight ratio, and triethanolamine solution is the dipropylene glycol solution that trolamine content accounts for 33%.
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) by the weight parts of component, take polyether polyol mixtures 100 parts, diphenylmethanediisocyanate 125 parts, whipping agent 20 parts, composite catalyst 1.5 parts, suds-stabilizing agent 2 parts, linking agent 1 part and compound flame retardant 30 parts, polyether polyol mixtures, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, stirs and obtain A material; Wherein composite catalyst is that the triethylene diamine of 1.5:1 and dibutyl tin laurate compound obtain by weight ratio, triethylene diamine is the dipropylene glycol solution of triethylene diamine content 33%, and compound flame retardant is the dimethyl methyl phosphonate of 1:0.5 and urea is composite obtains by weight ratio.
(2) diphenylmethanediisocyanate and A material are heated up, temperature controls between 32 ~ 35 DEG C, and be in the environment of 32 ~ 35 DEG C, diphenylmethanediisocyanate is added in A material in temperature, then material is stirred, stir speed (S.S.) is 4500r/min, churning time 18s, pour into again in mould carry out foaming, slaking and releasing process, wherein, foaming condition is: temperature is 28 DEG C, relative humidity is 50%.
(3) foam of depanning carries out post curing treatment, the curing temperature 95 DEG C of post curing, curing time 10h.
Embodiment 5
Prepare raw material that halogen-free flame-retardant rigid urethane foam uses as following table 5:
Table 5
In table 5, compound flame retardant is the low polyphosphate of 1:1.5 and urea is composite obtains by weight ratio; Polyether polyol mixtures is polyethers 403 and the Polyether 220 of 1:1 by weight ratio, composite catalyst by weight ratio be 2.5:1 N ?crassitude solution and potassium oleate compound obtain, N ?crassitude solution be N ?crassitude content account for 33% dipropylene glycol solution.
Hensel steps 5005 product descriptions:
Density (25 DEG C of g/cm3): 1.23
Viscosity (25 DEG C of cps): 220
Nco value (%): 30.75
Acid number (ppm, HCL): 50 ?200
Hydrolysis chlorine (ppm, CI): <2000
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyether polyol mixtures, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out mix and blend, stir and obtain A material;
(2) polymethylene multi-phenenyl isocyanate 5005 and A material are heated up, temperature controls between 20 ~ 22 DEG C, and be in the environment of 20 ~ 22 DEG C, polymethylene multi-phenenyl isocyanate is added in A material in temperature, then material is stirred, stir speed (S.S.) is 4000r/min, churning time 12s, pour into again in mould carry out foaming, slaking and releasing process, wherein, foaming condition is: temperature is 26 DEG C, relative humidity is 35%;
(3) foam of depanning carries out post curing treatment, the curing temperature 85 DEG C of post curing, curing time 6h.
Table 6
Table 6 is the design parameter of polyvalent alcohol used in above-mentioned example.
Test the performance of the halogen-free flame-retardant rigid urethane foam of above-described embodiment 1 ~ 5 gained, test result is as following table 7:
Table 7
Determination of conductive coefficients: measure according to GB/T10294-2008, sample size is 200mm × 200mm × 25mm.
Horizontal vertical combustion testing: according to UL94 standard testing, sample size 125mm × 13mm × 0.75mm.
Oxygen index is tested: measure according to GB/T2406.2-2009, sample size 150mm × 10mm × 10mm.
Compressive strength test: according to GB/T8813 ?2008 standard tests, sample size 50mm × 50mm × 50mm.
Water-intake rate test: according to GB/T8810 ?2005 standard tests, sample size is 150mm × 150mm × 30mm.
Halogen gas measure: according to ISO5660 ?2002 standards carry out taper calorimetry, sample size is 200mm × 200mm × 25mm.
As shown in Table 7, invention product has superior flame retardant properties, adding a small amount of compound flame retardant just makes single vertical burn by combustion testing, and oxygen index is had very significantly improve, add 20 parts of compound flame retardants and oxygen index just can be made to reach more than 26.While lifting polyurethane foam flame retardant properties, adding of compound flame retardant does not have very large infringement to the physicals of foam, the compressive strength of pure hard polyurethane foam is 290KPa, and after adding the fire retardant of different deal, slight decline just appears in compressive strength; Owing to adding more water in embodiment 2, cause its compressive strength to decline at most, but its obtained foam can meet the requirement in GB/T21558-2008 " building insulation urethane foam ", compressive strength being more than or equal to 180KPa.Water-intake rate can react the foam structure of foam to a certain extent.From the change of water-intake rate, adding of composite flame-retardant agent does not affect substantially on polyurethane foam structure.Usual phosphate ester flame retardants is liquid, has plastification to urethane foam, and its compressive strength can be caused when usage quantity is larger to decline to a great extent, and innovative point of the present invention is the composite of phosphate ester flame retardants and urea.The physicals impact of the compound flame retardant obtained on urethane foam is small, does not almost have, ensure that urethane foam has good physicals; Its possible reason is that urea is linked in polyurethane foam main chain as reactive flame retardant or small molecule chain extender reaction, effectively can ensure the thermal and insulating performance of urethane foam, and can further improve the physical and mechanical property of urethane foam.In addition, the intervention of halogen in the raw material used, product can not pollute environment, has the feature of environmental protection.
The content mentioned in above-described embodiment is not limitation of the invention, and under the prerequisite not departing from inventive concept of the present invention, any apparent replacement is all within protection scope of the present invention.
Claims (9)
1. a halogen-free flame-retardant rigid urethane foam, it is characterized in that: in mass fraction, its composition of raw materials is: polyol blends 100 parts, polyisocyanates 105 ~ 180 parts, composite halogen-free flame retardants 20 ~ 80 parts, whipping agent 1 ~ 50 part, composite catalyst 1 ~ 3 part, suds-stabilizing agent 2 ~ 4 parts and linking agent 1 ~ 2 part;
The molecular-weight average of described polyol blends is 200 ~ 600g/mol, hydroxyl value is 300 ~ 800mgKOH/g, the viscosity of temperature 25 DEG C time is 2000 ~ 6000mPas;
Described composite halogen-free flame retardants is 1:(0.5 ~ 1.5 by weight ratio) phosphate ester flame retardants and urea is composite forms;
Described whipping agent is butane, pentamethylene, Skellysolve A, iso-pentane, 1,1,1,2 ?Tetrafluoroethane, 1,1,1,3,3 ?pentafluoropropane, 1,1,1,3,3 ?one or more in 3-pentafluorobutane and water;
Described composite catalyst is be (1.5 ~ 3) by mass ratio: the tertiary amine catalyst of 1 and organometallic compound composite and obtain;
Described suds-stabilizing agent is type siloxane suds-stabilizing agent;
Described linking agent is glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6 ?any one or more in dihydroxyhexane, trolamine, tri-isopropanolamine, tetramethylolmethane and polyether-tribasic alcohol.
2. halogen-free flame-retardant rigid urethane foam according to claim 1, is characterized in that: described polyvalent alcohol be in polyether glycol and polyester polyol one or more.
3. halogen-free flame-retardant rigid urethane foam according to claim 1, is characterized in that: described polyisocyanates is any one in a kind of in diphenylmethanediisocyanate and polymethylene multi-phenenyl isocyanate or their modifier.
4. halogen-free flame-retardant rigid urethane foam according to claim 1, is characterized in that: described phosphate ester flame retardants is any one or more in dimethyl methyl phosphonate, diethyl ethylphosphate, propyl group dimethyl phosphate, ISOPROPYL PHENYL DIPHENYL PHOSPHATE, triethyl phosphate, tricresyl phosphate (butoxyethyl group) ester, triphenylphosphate, Tritolyl Phosphate, Resorcinol two (diphenyl phosphoester) and low polyphosphate.
5. halogen-free flame-retardant rigid urethane foam according to claim 1, it is characterized in that: described tertiary amine catalyst is triethylamine, triethylene diamine, N, N ?diethylethanolamine, N, N ?dimethylethanolamine, dimethylaminoethoxyethanol, trolamine, trimethyl hydroxyethylammonium propylene diamine, trimethyl hydroxyethylammonium quadrol, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohol, tri-isopropyl amine, tri-isopropanolamine, Tributylamine, two (dimethylaminoethyl) ether, N, N ?dimethylcyclohexylamine, five methyl diethylentriamine, Tetramethyl Ethylene Diamine, 4-methyl hexamethylene diamine, 2, 4, 6 ?three (dimethylamino methyl) phenol, 1, 3, 5 ?three (dimethylamino-propyl) Hexahydrotriazine, N ?ethyl morpholine, N ?methylpiperazine, N ?crassitude, N ?picoline, N ?Methylimidazole, N, N ?any one or more in dimethyl benzylamine and three (dimethylamino-propyl) amine.
6. halogen-free flame-retardant rigid urethane foam according to claim 1, is characterized in that: described organometallic compound is any one or more in dibutyl tin laurate, stannous octoate, tin acetate, dibutyltin diacetate, dioctyl tin diacetate, two (dodecyl sulphur) dibutyl tin, isocaprylic acid potassium, Potassium ethanoate and potassium oleate.
7. a preparation method for the halogen-free flame-retardant rigid urethane foam according to any one of claim 1 ?6, is characterized in that comprising the following steps:
(1) polyol blends, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and composite halogen-free flame retardants are carried out mix and blend, mix and obtain A material;
(2) polyisocyanates and described A are expected control temperature is 20 ~ 35 DEG C respectively, in the environment of 20 ~ 35 DEG C, polyisocyanates is added in A material, then material is stirred, then pour in mould and carry out foaming and the demoulding;
(3) foam of depanning carries out post curing treatment, the curing temperature 80 ~ 100 DEG C of post curing, curing time 4 ~ 12h.
8. the preparation method of halogen-free flame-retardant rigid urethane foam according to claim 7, is characterized in that: the temperature of described foaming is 25 ~ 30 DEG C, relative humidity is 25 ~ 60%.
9. the preparation method of halogen-free flame-retardant rigid urethane foam according to claim 7, is characterized in that: the speed of step (2) described stirring is 3000 ~ 4500r/min, the time of stirring is 10 ~ 20s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669741.4A CN103694438B (en) | 2013-12-10 | 2013-12-10 | A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669741.4A CN103694438B (en) | 2013-12-10 | 2013-12-10 | A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103694438A CN103694438A (en) | 2014-04-02 |
| CN103694438B true CN103694438B (en) | 2015-10-28 |
Family
ID=50356115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310669741.4A Active CN103694438B (en) | 2013-12-10 | 2013-12-10 | A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103694438B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992353B (en) * | 2014-05-04 | 2016-06-08 | 常州大学 | Fire retardant six butanol basic ring three phosphonitrile and preparation method and application |
| CN104072715B (en) * | 2014-07-07 | 2016-09-28 | 旭川化学（苏州）有限公司 | Solvent-free environment-friendly polyurethane automobile leather foaming layer resin and its preparation method and application |
| CN105273217A (en) * | 2014-07-14 | 2016-01-27 | 杭州金松优诺电器有限公司 | HFC-245fa ternary foaming agent-based thermal insulation material and filling technology |
| CN104211907A (en) * | 2014-09-05 | 2014-12-17 | 临夏市能成古典建筑装饰工程有限责任公司 | PU material for producing brick carvings and preparation method of PU material |
| CN104231210A (en) * | 2014-09-28 | 2014-12-24 | 江阴奥派交通装备有限公司 | Panel material of cab of high-speed train and preparation method of panel material |
| CN104927023A (en) * | 2014-11-06 | 2015-09-23 | 上海世富环保节能科技股份有限公司 | High-performance hard-foam polyurethane heat insulating material for exterior walls |
| CN105330802B (en) * | 2015-12-11 | 2018-01-19 | 南京林业大学 | A kind of Turpentine catalysts for polyurethanes and its application |
| CN105440657B (en) * | 2016-01-13 | 2017-03-22 | 南阳理工学院 | External wall thermal insulation material and preparation method thereof |
| CN105969138B (en) * | 2016-04-27 | 2018-04-10 | 江苏百代节能建材有限公司 | The external-wall heat-insulation material and coating of a kind of fire-proof and damp-proof |
| CN105860507A (en) * | 2016-05-20 | 2016-08-17 | 苏州倍力特物流设备有限公司 | High-efficiency flame-retardant foamed plastic and preparation method thereof |
| CN106117490A (en) * | 2016-08-03 | 2016-11-16 | 南宁可煜能源科技有限公司 | A kind of building polyurethane foamed material |
| CN106146786A (en) * | 2016-08-03 | 2016-11-23 | 南宁可煜能源科技有限公司 | High performance polyurethane exterior wall foamed materials |
| CN106243308A (en) * | 2016-08-25 | 2016-12-21 | 谢松芬 | Building polyurethane foamed material |
| CN106243695A (en) * | 2016-08-25 | 2016-12-21 | 谢松芬 | High performance polyurethane exterior wall foamed materials |
| CN106892678A (en) * | 2017-02-24 | 2017-06-27 | 玉林龙升建筑装饰工程有限公司 | A kind of porous ceramics and preparation method thereof |
| CN107141443A (en) * | 2017-04-19 | 2017-09-08 | 广州朗腾聚氨酯有限公司 | A kind of flame retarding polyether composition and its preparation method and application |
| CN107434846A (en) * | 2017-09-20 | 2017-12-05 | 贵州航天天马机电科技有限公司 | A kind of high temperature resistant hard polyurethane foam material and preparation method thereof |
| CN107814901B (en) * | 2017-11-29 | 2020-03-03 | 中原工学院 | Preparation method of metal modified phenolic polyurethane foam |
| CN108948422B (en) * | 2018-07-25 | 2020-04-07 | 浙江万盛股份有限公司 | Composite flame retardant, preparation method and application thereof, and polyurethane foam |
| CN109485899A (en) * | 2018-09-25 | 2019-03-19 | 青岛世林新海绵有限公司 | Halogen-free flameproof foam and preparation method thereof |
| CN109503794B (en) * | 2018-11-13 | 2021-08-17 | 江苏奥斯佳材料科技股份有限公司 | Polyurethane rigid foam composition, polyurethane rigid foam material and preparation method thereof |
| CN109705390A (en) * | 2018-12-29 | 2019-05-03 | 南京师范大学 | A kind of Halogen ring-type pyrophosphate is preparing the application in flame retarded rigid polyurethane foams plastics |
| CN109864238A (en) * | 2019-03-06 | 2019-06-11 | 南京航空航天大学 | A kind of take out uses microwave disinfection cabinet |
| CN110407992A (en) * | 2019-06-11 | 2019-11-05 | 沈阳理工大学 | A kind of the material preparation and application of flame retardant polyurethane rigid foam |
| CN110790986B (en) * | 2019-11-20 | 2021-07-30 | 山东柯帷博伟耐火材料有限公司 | Sugar resin thermal insulation material and preparation and recycling thereof |
| CN110862501B (en) * | 2019-12-03 | 2021-11-23 | 南京红宝丽新材料有限公司 | Polyurethane rigid foam plastic for covering austenitic stainless steel and preparation method thereof |
| CN111072915A (en) * | 2019-12-11 | 2020-04-28 | 山东省海洋化工科学研究院 | Polyurethane foam composition and method for preparing polyurethane foam by using same |
| CN111978505A (en) * | 2020-09-14 | 2020-11-24 | 江苏金宇防腐科技有限公司 | Water-based light foaming material and production method thereof |
| CN113321781A (en) * | 2021-05-28 | 2021-08-31 | 玖龙智能包装(东莞)有限公司 | Pressure-resistant heat-insulating material, preparation method thereof and corrugated case |
| CN113402770B (en) * | 2021-07-08 | 2023-03-24 | 上海鹤城高分子科技有限公司 | Method for degrading, recycling and reusing polyurethane |
| CN114940819A (en) * | 2021-11-24 | 2022-08-26 | 上海联景高分子材料有限公司 | Novel flame-retardant anti-aging thermoplastic polyurethane elastomer and preparation method thereof |
| CN114231018A (en) * | 2022-01-04 | 2022-03-25 | 广东五恒新材料有限公司 | Heat insulation composite material for bridge-cut-off aluminum alloy profile, bridge-cut-off aluminum alloy profile and preparation method of bridge-cut-off aluminum alloy profile |
| CN114133528B (en) * | 2022-01-04 | 2024-02-02 | 广东五恒新材料有限公司 | Polyurethane material for building door and window section bar, building door and window section bar and preparation method thereof |
| CN114940005A (en) * | 2022-07-04 | 2022-08-26 | 张家港飞腾复合新材料股份有限公司 | High-heat-insulation heat-preservation composite board and production process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423250B1 (en) * | 1996-09-30 | 2002-07-23 | David H. Blount | Flame retardant compositions utilizing a mixture of cyanuric acid and cyamelide compounds |
| DE20303672U1 (en) * | 2003-03-03 | 2004-04-15 | Polymerics Gmbh | Halogen-free, flame-retardant, hard polyurethane foam, useful e.g. for sealing gaps in buildings, contains a synergistic mixture of ABC-extinguishing powder and expanded graphite |
| CN101724254A (en) * | 2009-12-09 | 2010-06-09 | 顺德职业技术学院 | Efficient halogen-free anti-inflaming polyurethane hard foam and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7129291B2 (en) * | 1996-09-30 | 2006-10-31 | Blount David H | Flame retardant urea-bio based urethane compositions |
-
2013
- 2013-12-10 CN CN201310669741.4A patent/CN103694438B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423250B1 (en) * | 1996-09-30 | 2002-07-23 | David H. Blount | Flame retardant compositions utilizing a mixture of cyanuric acid and cyamelide compounds |
| DE20303672U1 (en) * | 2003-03-03 | 2004-04-15 | Polymerics Gmbh | Halogen-free, flame-retardant, hard polyurethane foam, useful e.g. for sealing gaps in buildings, contains a synergistic mixture of ABC-extinguishing powder and expanded graphite |
| CN101724254A (en) * | 2009-12-09 | 2010-06-09 | 顺德职业技术学院 | Efficient halogen-free anti-inflaming polyurethane hard foam and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 全水发泡非卤阻燃聚氨酯硬质泡沫塑料的制备与性能;陈一民等;《聚氨酯工业》;20070228(第01期);第24-27页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103694438A (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103694438B (en) | A kind of halogen-free flame-retardant rigid urethane foam and preparation method thereof | |
| CN112239531B (en) | Full-water combined polyether, high-flame-retardant LNG polyurethane block foam derived from full-water combined polyether and preparation method of polyurethane block foam | |
| CN104017154B (en) | Electric water heater combined polyether, urethane and feedstock composition and preparation method thereof | |
| CN103183806B (en) | A kind of High-flame-retardanthard hard polyurethane foam and preparation method thereof | |
| CN103665305B (en) | High-fire-resistance polysiocyanurate rigid foams and preparation method thereof | |
| CN102558479B (en) | Premixed polyether for polyisocyanurate foam and using method thereof | |
| CN101012332B (en) | Lignin and waste rigid foam powder fluorine-free polyurethane heat insulation material and preparing method | |
| CN105884992A (en) | Flame-retardant polyurethane rigid foam plastic and preparation method and application thereof | |
| CA2841878C (en) | Polyol composition for rigid polyurethane foam and production method for rigid polyurethane foam | |
| CN103709432B (en) | A kind of high flame retardant rigid urethane foam and preparation method thereof | |
| CN105461895B (en) | Combined polyether, polyisocyanurate foam and its feedstock composition and preparation method | |
| CN103923294A (en) | Preparation of single-component fire retardation polyurethane foam sealant | |
| CN102911334A (en) | B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam | |
| CN109438649B (en) | Heat insulation material for flame-retardant combined polyether and polyisocyanurate board and preparation method thereof | |
| CN104497251A (en) | Combined polyether, polyisocyanurate foam and preparation method thereof | |
| CN103788622B (en) | A kind of nanoparticle fire retardant modified rigid polyurethane PIR foam materials and preparation method thereof | |
| CN105669937A (en) | Environment-friendly flame-retardant hard polyurethane foaming plastic | |
| CN107033317A (en) | A kind of hard polyurethane foam material and preparation method and application | |
| CN109400839B (en) | Flame-retardant combined polyether, flame-retardant polyisocyanurate foam and preparation method thereof | |
| CN106674482A (en) | Polyurethane spraying composition material used for low temperature, cold insulation and flame retardance and preparation method of polyurethane spraying composition material | |
| CN106167540A (en) | Continuous way produces polyurethane plate high fire-retardance combined polyether and preparation method thereof | |
| CN104927022A (en) | Halogen-free inherent flame retardant type RPUF (Rigid Polyurethane Foam) and preparation method thereof | |
| CN104829823A (en) | Preparation method and application of flame-retardant polyol | |
| CN105859999A (en) | High-flame-retardation PIR-system polyurethane thermal-insulation material and preparation method thereof | |
| CN104356349A (en) | Flame-retardant type polyurethane hard foam material as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |