CN103694438A - Halogen-free flame-retardant rigid polyurethane foamed plastic and preparation method for same - Google Patents
Halogen-free flame-retardant rigid polyurethane foamed plastic and preparation method for same Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- 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
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- 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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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- 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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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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 halogen-free flame-retardant rigid polyurethane foamed plastic and a preparation method for the same. The polyurethane foamed plastic consists of the following raw materials in parts by weight: 100 parts of polyalcohol mixture, 105 to 180 parts of polyisocyanate, 20 to 80 parts of compound halogen-free flame retardant, 1 to 50 parts of foaming agent, 1 to 3 parts of composite catalyst, 2 to 4 parts of foam stabilizer and 1 to 2 parts of cross-linking agent. An obtained product is high in flame retardance and environment-friendly, the raw materials are free of halogen, and the production of toxic gas such as hydrogen halide during combustion is avoided; the raw materials are readily available and low in cost, so that the preparation cost of the polyurethane foamed plastic is greatly lowered; the polyurethane foamed plastic also has the characteristic of wide application range, and is applied to cold storage and heat-preservation industries of external wall heat-preservation of buildings, heat-preservation of pipelines, refrigerators, freezers and the like.
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 has been subject to paying attention to widely and has developed rapidly, and it can partly replace timber, metal and other plastics, and range of application is almost penetrated 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 flouring, so not only can cause huge financial loss, even also can cause loss of life and personal injury, non-flame-retardant polyurethane porous plastics 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 Flame Retardancy can be declined in the liquid flame retardant in material.Traditional Halogen phosphate flame retardant, from polymeric system spins off, is difficult for degraded and environment is caused to tremendous influence, discharges hydrogen halide and has pungency, corrodibility, serious threat people's the security of the lives and property in combustion processes.Another kind is the reaction-type flame-retarding material that contains flame retarding construction in molecular structure, reaction-type flame-retarding is that the structures such as ignition-proof element phosphorus, halogen, nitrogen or phenyl ring are imported in polyol structure at the same time or separately by chemical reaction, and makes 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 contain flame-retardant composition, can in life-time service process, not separate out and reduces 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, when having guaranteed good 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.
Halogen-free flame-retardant rigid urethane foam: in a mass fraction, its composition of raw materials is: 1～2 part of 100 parts of polyol blends, 105～180 parts of polyisocyanates, 20～80 parts of composite halogen-free flame retardantss, 1～50 part of whipping agent, 1～3 part of composite catalyst, 2～4 parts of suds-stabilizing agents and linking agent;
The molecular-weight average of described polyol blends is that 200～600g/mol, hydroxyl value are that 300～800mgKOH/g, the viscosity of temperature in the time of 25 ℃ are 2000～6000MPas;
Described composite halogen-free flame retardants is 1:(0.5～1.5 by weight ratio) phosphoric acid ester fire retardant 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 to be (1.5～3) by mass ratio: 1 tertiary amine catalyst and organometallic compound are composite to be obtained;
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 trihydroxy-hexane, 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 in a kind of in diphenylmethanediisocyanate and polymethylene multi-phenenyl isocyanate or their modifier.
Described phosphoric acid ester fire retardant 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, dimethylamino ethoxy ethanol, trolamine, trimethylammonium hydroxyethyl propylene diamine, trimethylammonium hydroxyethylethylene diamine, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohols, 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, oxalic acid dioctyl tin, 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 to mix and blend, mix and obtain A material;
(2) polyisocyanates and described A are expected to controlling respectively temperature is 20～35 ℃, in the environment of 20～35 ℃, polyisocyanates is added in A material, then material is stirred, then pour in mould and foam and the demoulding;
(3) foam of depanning carries out post curing treatment, 80～100 ℃ of the curing temperatures of post curing, curing time 4～12h.
The temperature of described foaming is preferably 25～30 ℃, relative humidity and is preferably 25～60%.
The time that the speed of the described stirring of step (2) is preferably 3000～4500r/min, 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 guarantee thermal and insulating performance and the dimensional stability of urethane foam simultaneously.Polyvalent alcohol is selected from one or more in polyether glycol and polyester polyol, preferably molecular-weight average is 200～600g/mol, hydroxyl value is 300～800mgKOH/g, the polyol blends that the viscosity of temperature in the time of 25 ℃ is 2000～6000MPas, more preferably hydroxyl value is 350～700mgKOH/g, the polyol blends that the viscosity of temperature in the time of 25 ℃ is 2000～5000MPas, most preferably hydroxyl value is 400～600mgKOH/g, the polyol blends that the viscosity of temperature in the time of 25 ℃ is 2000～4000MPas, specifically can be 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 2～5 polymethylene multi-phenenyl isocyanate, the polymethylene multi-phenenyl isocyanate that more preferably functional group's degree is 3～4, is specially any 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 completely, thereby improves the physical and mechanical property of urethane foam.
The present invention adopts by phosphoric acid ester fire retardant and the composite composite halogen-free flame retardants forming of urea, and the weight ratio of phosphoric acid ester fire retardant 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 on the physical and mechanical property impact of urethane foam by the composite compound flame retardant obtaining, almost do not have, thereby guaranteed that urethane foam has good physical and mechanical property; In the present invention, urea can be regarded reactive flame retardant and small molecule chain extender as, can effectively guarantee the thermal and insulating performance of urethane foam, and can further improve the physicals of urethane foam; In addition, phosphoric acid ester fire retardant and urea have good cooperative flame retardant effect, make the oxygen index of prepared urethane foam arrive 30 left and right.The above-mentioned phosphoric acid ester fire retardant of mentioning 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 polyphosphates, role is similar in the present invention for the above-mentioned material of mentioning, can mutually replace using, and can be separately a kind of composite with urea, also optional wherein several carry out composite use.
In the present invention, the mentioned material of whipping agent can independent a kind of use, and also optional several mixing are wherein used, and when elected water mixes use with other materials, foaming effect is better, is more preferably water and uses separately.Selected whipping agent has lower boiling point and higher vapour pressure, also can improve the performance of urethane foam under cold condition, when several being used in combination, urethane foam has larger mechanical property in certain temperature range, and can further improve the heat conductivility of plastics.
When water is used separately, with the polyol blends metering 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 or/and iso-pentane mix while using, the usage quantity selection range of water is identical while using separately as water, pentamethylene, Skellysolve A are or/and the usage quantity of iso-pentane, with respect to the polyol blends of 100 parts by weight, is 10～30 parts preferably.
When water and 1,1,1,3,3 ?pentafluoropropane, 1,1,1,3,3 ?during 3-pentafluorobutane, the usage quantity of water is preferably 1～5 with respect 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 with respect to the polyol blends of 100 mass parts, be preferably 20～50 parts.
In the present invention, composite catalyst is composite and obtain by tertiary amine catalyst and organometallic compound, the mass ratio of tertiary amine catalyst and organometallic compound is (1.5～3): 1, composite catalyst can well promote amine esterification, foaming process is had to high catalytic activity and selectivity, there is stronger foaming effect simultaneously, can improve the mobility of foam, be conducive to the preparation of urethane foam.Tertiary amine catalyst is triethylamine, triethylene diamine, N, N ?diethylethanolamine, N, N ?dimethylethanolamine, dimethylamino ethoxy ethanol, trolamine, trimethylammonium hydroxyethyl propylene diamine, trimethylammonium hydroxyethylethylene diamine, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohols, 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 several combination in dimethyl benzylamine and three (dimethylamino-propyl) amine, role is similar in the present invention for the above-mentioned material of mentioning, can mutually replace using, described organometallic compound is any one or several combination in dibutyl tin laurate, stannous octoate, tin acetate, dibutyltin diacetate, oxalic acid dioctyl tin, 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 of mentioning, 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, can reduce the surface tension of urethane raw mixture, at foam, be raised up between the maturation period, by surface tension, prevent that the material of the thermodynamics unstable state appearance of foam from all can select.In order to give product heat-proof quality, can specifically 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 and is obtained by Nanjing Dymatic Shichuang Chemical Co., Ltd..
In the present invention, the present invention has linking agent to select glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6 ?any one or several combination in trihydroxy-hexane, trolamine, tri-isopropanolamine, tetramethylolmethane and polyether-tribasic alcohol, the interpolation of linking agent has improved the cross-linking density of foam effectively in addition, prevent the cracking of foam in urethane foam preparation process, also improved the hardness of urethane foam simultaneously.
Each parameter of controlling in the preparation method of urethane foam of the present invention is to pass through test of many times gained according to the difference of components by weight, and the selection of parameter is applicable to the performance of urethane foam of the present invention.
With respect to prior art, tool of the present invention has the following advantages:
1) the present invention is undertaken compositely by phosphoric acid ester fire retardant and urea, and the compound flame retardant obtaining is small on the physicals impact of urethane foam, does not almost have, thereby has guaranteed that urethane foam has good physicals; Urea can be regarded reactive flame retardant and small molecule chain extender as, can effectively guarantee the thermal and insulating performance of urethane foam, and can further improve the physical and mechanical property of urethane foam; In addition, phosphoric acid ester fire retardant and urea have good cooperative flame retardant effect, make the oxygen index of prepared urethane foam arrive 30 left and right.
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 using 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 having wide range of applications, and specifically can be the cold-storage insulation industries such as building exterior wall heat preserving, piping insulation, refrigerator.
Embodiment
For understanding better the present invention, below by 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, the dimethyl methyl phosphonate that compound flame retardant is 1:0.5 by weight ratio and urea are composite to be obtained; Polyethers 4110 and polyethers 4110H that polyol blends is 2.5:1 by weight ratio form, and particular case is in Table 6; The triethylene diamine solution that composite catalyst is 1.5:1 by weight ratio and dibutyl tin laurate is compound obtains, triethylene diamine solution is that triethylene diamine mass content accounts for 33% dipropylene glycol solution.
In the present embodiment, butane also can be 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 glycol mixture, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out to mix and blend, stir and obtain A material;
(2) diphenylmethanediisocyanate and A material are heated up, temperature is controlled between 20～25 ℃, and in temperature is the environment of 20～25 ℃, diphenylmethanediisocyanate is added in A material, then material is stirred, stir speed (S.S.) is 3000r/min, churning time 10s, pour in mould again foam, slaking and releasing process, wherein, foaming condition is: temperature is that 25 ℃, relative humidity are 25%;
(3) foam of depanning carries out post curing treatment, 80 ℃ of the curing temperatures 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 glycol mixture | 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, the triethyl phosphate that compound flame retardant is 1:0.8 by weight ratio and urea are composite to be obtained; Polyethers 4110 and polyethers 4110H that polyether glycol mixture is 1.5:1 by weight ratio form, and particular case is in Table 6; The N that composite catalyst is 1.5:1 by weight ratio, N ?diethylethanolamine solution and stannous octoate is compound obtains, N, N ?diethylethanolamine solution be N, N ?diethylethanolamine mass content account for 33% dipropylene glycol solution.
Polymeric MDI MR ?200 fundamental propertys:
The place of production: Japanese Ruian
Isocyanate content (Wt%): 30 ?32
Viscosity (mPas/25 ℃): 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 glycol mixture, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out to mix and blend, stir and obtain A material; The triethylene diamine that wherein composite catalyst is 1.5:1 by weight ratio and dibutyl tin laurate is compound obtains, triethylene diamine is the dipropylene glycol solution of triethylene diamine content 33%, and the dimethyl methyl phosphonate that compound flame retardant is 1:0.5 by weight ratio and urea are composite to be obtained;
(2) to MR ?200 and A material heat up, temperature is controlled between 25～30 ℃, and temperature be in the environment of 25～30 ℃ by MR ?200 add in A material, then material is stirred, stir speed (S.S.) is 3500r/min, churning time 20s, pour in mould again foam, slaking and releasing process, wherein, foaming condition is: temperature is that 28 ℃, relative humidity are 40%;
(3) foam of depanning carries out post curing treatment, 90 ℃ of the curing temperatures 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, the triphenylphosphate that compound flame retardant is 1:1.2 by weight ratio and urea are composite to be obtained; Polyethers 4110 and polyethers 4110H that polyether glycol mixture is 1:1 by weight ratio form, particular case is in Table 6, the triethanolamine solution that composite catalyst is 3:1 by weight ratio and isocaprylic acid potassium is compound obtains, triethanolamine solution is that trolamine mass content accounts for 33% dipropylene glycol solution.
MDI3051 fundamental property:
Outward appearance: colourless transparent liquid
Density (25 ℃, g/cm3): 1.22
NCO content: 33.6%
Viscosity (25 ℃, mPa.s): 14
Vapour pressure (25 ℃, mmHg): <0.00001
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) polyether glycol mixture, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out to mix and blend, stir and obtain A material;
(2) MDI3051 and A material are heated up, temperature is controlled between 30～35 ℃, and in temperature is the environment of 30～35 ℃, MDI3051 is added in A material, then material is stirred, stir speed (S.S.) is 4000r/min, churning time 20s, pour in mould again foam, slaking and releasing process, wherein, foaming condition is: temperature is that 30 ℃, relative humidity are 60%;
(3) foam of depanning carries out post curing treatment, 100 ℃ of the curing temperatures of post curing, curing time 12h.
Embodiment 4
The present embodiment is prepared raw material that halogen-free flame-retardant rigid urethane foam uses as following table 4:
Table 4
In table 4, the Tritolyl Phosphate that compound flame retardant is 1:1.3 by weight ratio and urea are composite to be obtained; Polyethers 835 and polyethers 888 that polyether glycol mixture is 1:1 by weight ratio form, particular case is in Table 6, the triethanolamine solution that composite catalyst is 3:1 by weight ratio and tin acetate are compound to be obtained, and triethanolamine solution is that trolamine content accounts for 33% dipropylene glycol solution.
A preparation method for halogen-free flame-retardant rigid urethane foam, comprises the following steps:
(1) by the parts by weight of component, take 30 parts of 100 parts, polyether glycol mixture, 125 parts of diphenylmethanediisocyanates, 20 parts of whipping agents, 1.5 parts of composite catalysts, 2 parts of suds-stabilizing agents, 1 part of linking agent and compound flame retardants, polyether glycol mixture, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out to mix and blend, stir and obtain A material; The triethylene diamine that wherein composite catalyst is 1.5:1 by weight ratio and dibutyl tin laurate is compound obtains, triethylene diamine is the dipropylene glycol solution of triethylene diamine content 33%, and the dimethyl methyl phosphonate that compound flame retardant is 1:0.5 by weight ratio and urea are composite to be obtained.
(2) diphenylmethanediisocyanate and A material are heated up, temperature is controlled between 32～35 ℃, and in temperature is the environment of 32～35 ℃, diphenylmethanediisocyanate is added in A material, then material is stirred, stir speed (S.S.) is 4500r/min, churning time 18s, pour in mould again foam, slaking and releasing process, wherein, foaming condition is: temperature is that 28 ℃, relative humidity are 50%.
(3) foam of depanning carries out post curing treatment, 95 ℃ of the curing temperatures 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, the low polyphosphate that compound flame retardant is 1:1.5 by weight ratio and urea are composite to be obtained; Polyethers 403 and Polyether 220 that polyether glycol mixture is 1:1 by weight ratio, the N that composite catalyst is 2.5:1 by weight ratio ?crassitude solution and potassium oleate is compound obtains, N ?crassitude solution be N ?crassitude content account for 33% dipropylene glycol solution.
Hensel steps 5005 product descriptions:
Density (25 ℃ of g/cm3): 1.23
Viscosity (25 ℃ 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 glycol mixture, whipping agent, composite catalyst, suds-stabilizing agent, linking agent and Compositional type halogen-free flame retardants are carried out to mix and blend, stir and obtain A material;
(2) polymethylene multi-phenenyl isocyanate 5005 and A material are heated up, temperature is controlled between 20～22 ℃, and in temperature is the environment of 20～22 ℃, polymethylene multi-phenenyl isocyanate is added in A material, then material is stirred, stir speed (S.S.) is 4000r/min, churning time 12s, pour in mould again foam, slaking and releasing process, wherein, foaming condition is: temperature is that 26 ℃, relative humidity are 35%;
(3) foam of depanning carries out post curing treatment, 85 ℃ of the curing temperatures of post curing, curing time 6h.
Table 6
Table 6 is the design parameter of polyvalent alcohol used in above-mentioned example.
Performance to the halogen-free flame-retardant rigid urethane foam of above-described embodiment 1～5 gained is tested, and 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 test: measure sample size 150mm * 10mm * 10mm according to GB/T2406.2-2009.
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 is measured: 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, add a small amount of compound flame retardant just to make single vertical combustion can pass through combustion testing, and make oxygen index have very significantly raising, add 20 parts of compound flame retardants just can make oxygen index reach more than 26.When promoting polyurethane foam flame retardant properties, not adding of compound flame retardant has very large infringement to the physicals of foam, the compressive strength of pure hard polyurethane foam is 290KPa, adds after the fire retardant of different deals, and slight decline just appears in compressive strength; In embodiment 2 owing to adding more water, cause its compressive strength to decline at most, but its foam making can meet GB/T21558-2008 < < building insulation with in urethane foam > >, compressive strength being more than or equal to the requirement of 180KPa.Water-intake rate can react the foam structure of foam to a certain extent.From the variation of water-intake rate, adding of composite flame-retardant agent do not have impact substantially on polyurethane foam structure.Conventionally phosphoric acid ester fire retardant is liquid, and urethane foam is had to plastification, can cause its compressive strength to decline to a great extent, and innovative point of the present invention is the composite of phosphoric acid ester fire retardant and urea when usage quantity is larger.The compound flame retardant obtaining is small on the physicals impact of urethane foam, does not almost have, and has guaranteed 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, can effectively guarantee 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 using, product can not pollute environment, has the feature of environmental protection.
The content of mentioning in above-described embodiment is not limitation of the invention, is not departing under the prerequisite of inventive concept of the present invention, and 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: 1～2 part of 100 parts of polyol blends, 105～180 parts of polyisocyanates, 20～80 parts of composite halogen-free flame retardantss, 1～50 part of whipping agent, 1～3 part of composite catalyst, 2～4 parts of suds-stabilizing agents and linking agent;
The molecular-weight average of described polyol blends is that 200～600g/mol, hydroxyl value are that 300～800mgKOH/g, the viscosity of temperature in the time of 25 ℃ are 2000～6000MPas;
Described composite halogen-free flame retardants is 1:(0.5～1.5 by weight ratio) phosphoric acid ester fire retardant 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 to be (1.5～3) by mass ratio: 1 tertiary amine catalyst and organometallic compound are composite to be obtained;
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 trihydroxy-hexane, 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 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 phosphoric acid ester fire retardant 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, dimethylamino ethoxy ethanol, trolamine, trimethylammonium hydroxyethyl propylene diamine, trimethylammonium hydroxyethylethylene diamine, N, N ?two (dimethylamino-propyl) α-amino isopropyl alcohols, 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, oxalic acid dioctyl tin, two (dodecyl sulphur) dibutyl tin, isocaprylic acid potassium, Potassium ethanoate and potassium oleate.
7. according to a preparation method for the halogen-free flame-retardant rigid urethane foam described in claim 1 ?6 any one, it is characterized in that comprising 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 to mix and blend, mix and obtain A material;
(2) polyisocyanates and described A are expected to controlling respectively temperature is 20～35 ℃, in the environment of 20～35 ℃, polyisocyanates is added in A material, then material is stirred, then pour in mould and foam and the demoulding;
(3) foam of depanning carries out post curing treatment, 80～100 ℃ of the curing temperatures 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 that 25～30 ℃, relative humidity are 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 the described stirring of step (2) is that the time of 3000～4500r/min, stirring is 10～20s.
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