CN101906248B - High compression-strength rigid-enhancement type hard polyurethane foaming plastic and preparation method thereof - Google Patents
High compression-strength rigid-enhancement type hard polyurethane foaming plastic and preparation method thereof Download PDFInfo
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- CN101906248B CN101906248B CN2010102202207A CN201010220220A CN101906248B CN 101906248 B CN101906248 B CN 101906248B CN 2010102202207 A CN2010102202207 A CN 2010102202207A CN 201010220220 A CN201010220220 A CN 201010220220A CN 101906248 B CN101906248 B CN 101906248B
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- 238000005187 foaming Methods 0.000 title claims abstract description 70
- 239000004814 polyurethane Substances 0.000 title claims abstract description 70
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 35
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 58
- -1 glycol phthalates Chemical class 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 29
- 229920001228 polyisocyanate Polymers 0.000 claims description 29
- 239000005056 polyisocyanate Substances 0.000 claims description 29
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 17
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 210000002615 epidermis Anatomy 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012970 tertiary amine catalyst Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high compression-strength rapid-enhancement type hard polyurethane foaming plastic which comprises the following components in percentage by weight: 1 to 55 percent of component A, 1 to 60 percent of polyalcohol, 1 to 20 percent of foaming agent, 0 to 10 percent of catalyst, 0 to 10 percent of foam stabilizer, 0 to 30 percent of flame retardant and 1 to 60 percent of isocyanate, wherein the component A is aromatic compounds with the following structural formulas in the specification. The invention simultaneously discloses a preparation method of the hard polyurethane foaming plastic also. The hard polyurethane foaming plastic of the invention has high compression strength and size stability under the low temperature.
Description
Technical field
The present invention relates to the preparation method of a kind of large-scale LNGC with high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Background technology
Natural gas liquids (LNG) is through pressurization cooling or be cooled to-163 ℃ of liquid fuels that form with gaseous natural gas.The transportation of a large amount of LNG must be accomplished through the Large LNG boats and ships.In the Large LNG transport-ship, competitive two kinds of large cargo holds design is respectively spherical tank type and film-type.Thermal insulation layer is the important barrier that guarantees the security of Large LNG ship, and two kinds of cargo holds all need adopt heat-insulating material, reach the purpose of transporting safely.Therefore the polymer heat-insulating material that is used for the Large LNG ship has critical role.
In theory, the macromolecular material with high stability and low thermal conductivity all can be used for the adiabatic heat-insulation of LNG ship, for example polystyrene foamed plastics, phenolic foamed plastics, urethane foam and polyvinyl chloride foam etc.But; Because requiring of Large LNG ship security is high; When requiring especially that the polymer heat-insulating material has low thermal conductivity under the deep cooling condition; Also must have performances such as high compression-strength, high-dimensional stability, therefore only have the urethane of special construction and polyvinyl chloride foam can satisfy its request for utilization.
Zhu Lvmin etc. have described with the performance of spun glass and glass hollow bead Reinforced Rigid Polyurethane Foam (Zhu Lvmin, Liu Yijun: urethane foam, the third edition).Though the method with spun glass can effectively strengthen urethane foam, common complex process, and also the anisotropy of material difference is very big.For example Chinese patent 200610128243.9 and 200710144139.3 has been informed the method with spun glass and continuous fibre enhancement polyurethane porous plastics respectively, but the former only mentions that to apparent unit weight be 768kg/m
3Its vertical compression intensity of urethane foam can reach 65.1MPa, the latter does not then indicate the direction of compression testing.Though in this area, be that the polyvalent alcohol of initiator contains aromatic structure with the Tetra hydro Phthalic anhydride, the functionality of such polyvalent alcohol is merely 2, and is unhelpful to the compression performance that improves rigid olyurethane foam.
Summary of the invention
The technical problem that the present invention will solve provides a kind of urethane foam with high compression-strength and low temperature dimensional stability and preparation method thereof.
In order to solve the problems of the technologies described above; The present invention provides a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic, is made up of following component in percentage by weight: 4%～40% A component, 1%～60% polyvalent alcohol, 1%～20% whipping agent, 0%～10% catalyzer, 0%～10% suds-stabilizing agent, 0%～30% fire retardant, 1%～60% isocyanic ester;
Said A component is the aromatics with following structural formula:
Further improvement as high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention: polyvalent alcohol is polyether glycol and/or polyester polyol, and the hydroxyl value of said polyvalent alcohol is that 200～800KOH/mg, functionality are 2～8; The weight percentage of polyvalent alcohol is 10%～50%.More preferably: the hydroxyl value of polyvalent alcohol is that 300～600KOH/mg, functionality are 3～6; The weight percentage of polyvalent alcohol is 20%～40%.
Further improvement as high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention: whipping agent is at least a in water, HCFC class, hydrogen fluorohydrocarbon class and the hydro carbons, and wherein water is preferred whipping agent; Catalyzer is tertiary amine catalyst or organo-metallic catalyst, preferred tertiary amine catalyzer; Suds-stabilizing agent is an organic silicon surfactant, and organic silicon surfactant is ZGK 5-olefin oxide segmented copolymer; Fire retardant is halogenated phosphate based flame retardant or phosphoric acid ester fire retardant.
Further improvement as high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention: the HCFC class is 1,1-two chloro-1-fluoroethanes (141b), and hydrogen fluorohydrocarbon class is 1; 1,1,3; 3-pentafluoropropane (HFC-254fa), hydro carbons are paraffinic hydrocarbons, alkene or naphthenic hydrocarbon; Tertiary amine catalyst is triethylene diamine, N, N '-dimethylcyclohexylamine, two (2-dimethylaminoethyl) ether or triethylenediamine; Organic silicon surfactant is B8433, B8404, B8467, AK-8802, AK-8805 or AK-8807; The halogenated phosphate based flame retardant is four (2-chloroethyl) diethylidene ether bisphosphate, and the phosphoric acid ester fire retardant is a dimethyl methyl phosphonate.
Further improvement as high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention: paraffinic hydrocarbons is normal butane, Trimethylmethane or Skellysolve A, and said naphthenic hydrocarbon is pentamethylene.
Further improvement as high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention: isocyanic ester is poly methylene poly phenyl poly isocyanate (PAPI), and the weight percentage of isocyanic ester is 30%～55%.
In the present invention, preferable ratio is: A component 4%～10%, polyvalent alcohol 30%～40%, whipping agent 1%～10%, catalyzer 0.5%～2%, suds-stabilizing agent 0.5%～2%, fire retardant 4%～8%, isocyanic ester 40%～50%.
The present invention also provides the preparation method of above-mentioned high compression-strength rigid-enhancement type hard polyurethane foaming plastic simultaneously, may further comprise the steps:
1), with A component and polyvalent alcohol uniform mixing;
2), whipping agent, catalyzer, suds-stabilizing agent and fire retardant are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds in the polyvalent alcohol storage tank of polyurethane foaming machine, isocyanic ester joined in the isocyanic ester storage tank of polyurethane foaming machine;
4), with the isocyanic ester high speed uniform mixing in mixture in the polyvalent alcohol storage tank and the isocyanic ester storage tank; Be poured in the metal die then;
5), treat that foam reaction in the metal die finishes after, promptly foam solidifies and naturally fully after the cooling, the demoulding in room temperature (10～30 ℃) held 3 days, gets high compression-strength rigid-enhancement type hard polyurethane foaming plastic with the gained polyurethane foamed material.
High compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention is by the A component, the B component, and C component and D component are formed.Specific as follows: the B component is a polyvalent alcohol; The C component is made up of whipping agent, catalyzer, suds-stabilizing agent and fire retardant; The D component is an isocyanic ester.
The preparation method of high compression-strength rigid-enhancement type hard polyurethane foaming plastic of the present invention; In step 1),, can adopt type of heating to mix in order to accelerate mixed effect; The temperature of heating can evenly be dissolved in the B component with the A component and being as the criterion, and mixes postcooling to room temperature.
In the invention process; The contriver also once attempted introducing dihydroxyphenyl propane and contained aromatic structure; Reach the purpose that strengthens the urethane foam compressive strength, but increasing degree is limited, and horizontal, vertical compressive strength still can not satisfy the requirement of film-type LNG ship to the rigidity heat-insulating material.If continuing increases content of bisphenol A, gained urethane foam over-all properties can descend.
The present invention is through introducing the special fragrance ring structure in polyurethane component, thereby makes the over-all properties of the rigid urethane foam of gained can satisfy the performance requriements of Large LNG transport-ship.Rigid urethane foam of the present invention has characteristics such as high compression-strength, low temperature dimensional stability, low thermal conductivity, can use the polyurethane adiabatic heat-insulation material as the Large LNG transport-ship.
Embodiment
Following umber is weight part.
Embodiment 1: a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic,
The ratio of each component is following:
The A component: 4,10 parts of the two glycol phthalates of 4-oxygen;
The B component: polyether glycol SC-450, hydroxyl value is 450mgKOH/g, 390 parts;
C component: 3 parts of triethylene diamine catalyzer, 3 parts of B8433 silicon foams stablizers, 1,15 parts of 1-two chloro-1-fluoroethane (F141b) whipping agents, 2 parts in water (as whipping agent), 15 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 105 parts of poly methylene poly phenyl poly isocyanates.
As 4 of A component, the structural formula and the preparation method of the two glycol phthalates of 4-oxygen are following:
Weigh 4, the two Tetra hydro Phthalic anhydrides of 4-oxygen, terepthaloyl moietie, ratio is 1: 20 (mol ratio), joins in the reaction kettle that TM and condensing surface are housed, heating (120 ℃) stirs.Be cooled to room temperature, add strongly acidic cationic exchange resin CT275 (as catalyzer), add-on is 4,2% (mass ratio) of the two Tetra hydro Phthalic anhydrides of 4-oxygen.Stir down and be warming up to 185 ℃ gradually, keep this temperature to reflux about 10 hours, reduce to (GB1668-8) at 2 o'clock, stir down temperature of reaction kettle is reduced to room temperature to the acid number of reaction system.Emit material in the still, the solids removed by filtration catalyzer.The reaction mass of gained is with 4 volumes, 5% (mass ratio) aqueous sodium hydroxide solution agitator treating doubly, and standing demix is used 5% (mass ratio) aqueous sodium carbonate washing doubly of 2 volumes after isolating product again.Standing demix adds isolating product and is equipped with in the still kettle of TM and condensing surface, steams except that residual terepthaloyl moietie to cut in 150 ℃, decompression (vacuum tightness is 0.1MPa) to steam, and is cooled to 50 ℃.In 50 ℃, the gac that in the material of gained, adds inventory 1% (mass ratio) stirs after 1 hour and cools the temperature to room temperature.Discharging removes by filter gac, obtains 4 of purifying, the two glycol phthalates of 4-oxygen, and yield 85%, purity are 98%.
The preparation method of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 10 parts of A components and 90 parts of B component uniform mixing;
2), 17 parts of whipping agents, 3 parts of catalyzer, 3 parts of suds-stabilizing agents and 15 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds in the polyvalent alcohol storage tank (A storage tank) of polyurethane foaming machine, poly methylene poly phenyl poly isocyanate joined in the isocyanic ester storage tank (B storage tank) of polyurethane foaming machine;
4), with the high speed of the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank (greater than 6000 rev/mins) uniform mixing; Be poured into then in the irony mould;
5), question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Through detecting, the performance of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following: density is 40kg/m
3(ASTM D 1622-03), vertical compressive strength is 0.43MPa, and horizontal compression intensity is 0.39MPa (ASTM D1621-04), and thermal conductivity is 0.0252W/mK (GB/T 3399), and the linear dimension velocity of variation is 45 * 10 for (25 ℃～-196 ℃) vertically
-6, laterally be (25 ℃～-196 ℃) 41 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTM D 1692) from fire certainly.
Embodiment 2, a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic,
The ratio of each component is following:
The A component: 4,20 parts of the two glycol phthalates of 4-oxygen;
B component: 40 parts of polyether glycol ST-480 (hydroxyl value is 480mgKOH/g), 35 parts of polyether glycol PN-560 (hydroxyl value is 560mgKOH/g), 5 parts of polyether glycol TD-400 (hydroxyl value is 400mgKOH/g);
C component: 2 parts of triethylene diamine catalyzer, 2.5 parts of AK-8802 silicon foams stablizers, 9 parts of F141b whipping agents, 2 parts in water (as whipping agent), 15 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 105 parts of poly methylene poly phenyl poly isocyanates;
The preparation method of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 20 parts of A components and 80 parts of B component uniform mixing;
2), 11 parts of whipping agents, 2 parts of catalyzer, 2.5 parts of suds-stabilizing agents and 15 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds in the polyvalent alcohol storage tank (A storage tank) of polyurethane foaming machine, poly methylene poly phenyl poly isocyanate joined in the isocyanic ester storage tank (B storage tank) of polyurethane foaming machine;
4), with the high speed of the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank (greater than 6000 rev/mins) uniform mixing; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Through detecting, the performance of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following: density is 60kg/m
3(ASTM D 1622-03); Vertical compressive strength is 0,65MPa (ASTM D 1621-04), and horizontal compression intensity is 0.61MPa (ASTM D 1621-04); Thermal conductivity is 0.0281W/mK (GB/T 3399), and the linear dimension velocity of variation is 38 * 10 for (25 ℃～-196 ℃) vertically
-6, laterally be (25 ℃～-196 ℃) 40 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTM D 1692) from fire certainly.
Embodiment 3, a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic,
The ratio of each component is following:
The A component: 4,15 parts of the two glycol phthalates of 4-oxygen;
B component: 20 parts of polyether glycols 4110 (hydroxyl value is 400mgKOH/g), 40 parts of polyether glycol ST-481 (hydroxyl value is 481mgKOH/g), 15 parts of polyester polyol PS-3152 (hydroxyl value is 315mgKOH/g);
C component: 2 parts of triethylene diamine catalyzer, 2 parts of B8433 silicon foams stablizers, 2 parts in water, 12 parts of four (2-chloroethyl) diethylidene ether bis-phosphate flame retardants
D component: 102 parts of poly methylene poly phenyl poly isocyanates;
According to the above ratio A component and B component are mixed, add the C component and mix, inject the A storage tank of foaming machine.Poly methylene poly phenyl poly isocyanate is injected foaming machine B storage tank.According to the above ratio, the material in A, the B storage tank is poured in the irony mould after (greater than 6000 rev/mins) mix at a high speed.After question response finishes, i.e. after foam curing is also cooled off naturally fully, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, obtain high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Its performance is following: density is 80kg/m3 (ASTM D 1622-03); Vertical compressive strength is 0.75MPa (ASTMD 1621-04); Horizontal compression intensity is 0.69MPa (ASTM D 1621-04); Thermal conductivity is 0.0285W/mK (GB/T 3399), and the linear dimension velocity of variation is 31 * 10 for (25 ℃～-196 ℃) vertically
-6, laterally be (25 ℃～-196 ℃) 40 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTM D 1692) from fire certainly.
Embodiment 4, a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic,
The ratio of each component (mass ratio):
The A component: 4,15 parts of two phthalic acids of 4-oxygen-condensed ethandiol ester;
B component: 40 parts of polyether glycol GNE410 (hydroxyl value is 410mgKOH/g), 45 parts of polyether glycol PN-560 (hydroxyl value is 560mgKOH/g);
C component: 1.5 parts of triethylenediamines (catalyzer), 2.5 parts of B8466 silicon foams stablizers, 15 parts of pentanes (whipping agent), 12 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 104 parts of poly methylene poly phenyl poly isocyanates.
As 4 of A component, the structural formula and the preparation method of the two phthalic acid one condensed ethandiol esters of 4-oxygen are following:
Weigh 4, the two Tetra hydro Phthalic anhydrides of 4-oxygen, a condensed ethandiol, ratio is 1: 20 (mol ratio), joins in the reaction kettle that TM and condensing surface are housed, heating (120 ℃) stirs.Be cooled to room temperature, add strongly acidic cationic exchange resin CT275 (as catalyzer), add-on is 4,2% (mass ratio) of the two Tetra hydro Phthalic anhydrides of 4-oxygen.Stir down and be warming up to 185 ℃ gradually, keep this temperature to reflux about 10 hours, reduce to (GB1668-8) at 2 o'clock, stir down temperature of reaction kettle is reduced to room temperature to the acid number of reaction system.Emit material in the still, the solids removed by filtration catalyzer.Reaction mass is with 4 volumes, 5% (mass ratio) aqueous sodium hydroxide solution agitator treating doubly, and standing demix is used 5% (mass ratio) aqueous sodium carbonate washing doubly of 2 volumes after isolating product again.Standing demix is equipped with isolating product adding in the still kettle of TM and condensing surface, and in 180 ℃, decompression (vacuum tightness is 0.05MPa) steaming removes a residual condensed ethandiol to cut and steams, and is cooled to 50 ℃.In 50 ℃, the gac that in the material of gained, adds inventory 1% (mass ratio) stirs after 1 hour and cools the temperature to room temperature.Discharging removes by filter gac, obtains 4 of purifying, the two phthalic acid one condensed ethandiol esters of 4-oxygen, and yield 80%, purity are 97.8%.
The preparation method of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 15 parts of A components and 85 parts of B component uniform mixing;
2), 15 parts of whipping agents, 1.5 parts of catalyzer, 2.5 parts of suds-stabilizing agents and 12 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds in the polyvalent alcohol storage tank (A storage tank) of polyurethane foaming machine, poly methylene poly phenyl poly isocyanate joined in the isocyanic ester storage tank (B storage tank) of polyurethane foaming machine;
4), with the high speed of the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank (greater than 6000 rev/mins) uniform mixing; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Through detecting, the performance of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following: density is 50kg/m
3(ASTM D 1622-03), vertical compressive strength is that 0.48MPa, horizontal compression intensity are 0.43MPa (ASTM D1621-04), and thermal conductivity is 0.0296W/mK (GB/T 3399), and the linear dimension velocity of variation is 39 * 10 for (25 ℃～-196 ℃) vertically
-6, laterally be (25 ℃～-196 ℃) 40 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTMD 1692) from fire certainly.
Embodiment 5, a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic,
The ratio of each component is following:
The A component: 4,18 parts of the two phthalic acid one condensed ethandiol esters of 4-oxygen;
B component: 50 parts of polyether glycol GNE410 (hydroxyl value is 410mgKOH/g), 32 parts of polyester polyol PS-3152 (hydroxyl value is 315mgKOH/g);
C component: 1.5 parts in two (2-dimethylaminoethyl) ether, 3 parts of B8469 silicon foams stablizers, 10 parts of pentanes, 12 parts of four (2-chloroethyl) diethylidene ether bisphosphates;
D component: 105 parts of poly methylene poly phenyl poly isocyanates;
The preparation method of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 18 parts of A components and 82 parts of B component uniform mixing;
2), 10 parts of whipping agents, 1.5 parts of catalyzer, 3 parts of suds-stabilizing agents and 12 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds in the polyvalent alcohol storage tank (A storage tank) of polyurethane foaming machine, poly methylene poly phenyl poly isocyanate joined in the isocyanic ester storage tank (B storage tank) of polyurethane foaming machine;
4), with the high speed of the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank (greater than 6000 rev/mins) uniform mixing; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 5 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
Through detecting, the performance of high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following: density is 70kg/m
3(ASTM D 1622-03), vertical compressive strength is that 0.78MPa, horizontal compression intensity are 0.74MPa (ASTM D 1621-04), and thermal conductivity is 0.0290W/mK (GB/T 3399), and the linear dimension velocity of variation is 35 * 10 for (25 ℃～-196 ℃) vertically
-6, laterally be (25 ℃～-196 ℃) 37 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTM D 1692) from fire certainly.
The comparative example: by 4, the two glycol phthalates of 4-oxygen make 20 parts of dihydroxyphenyl propanes into for 20 parts with the A component among the embodiment 2; All the other are fully with embodiment 2.The performance of products therefrom is following:
Density is 60kg/m
3(ASTM D 1622-03); Vertical compressive strength is 0.58MPa (ASTM D 1621-04); Horizontal compression intensity is 0.54MPa (ASTM D 1621-04), and thermal conductivity is 0.0286W/mK (GB/T 3399), and the linear dimension velocity of variation is 43 * 10 for (25 ℃～-196 ℃) vertically
-6(ASTM D 696-03) laterally is (25 ℃～-196 ℃) 45 * 10
-6(ASTM D 696-03), flame retardant resistance is for put out (ASTM D 1692) from fire certainly.
Embodiment 2 contrasts with the salient features of the products therefrom of Comparative Examples
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1. high compression-strength rigid-enhancement type hard polyurethane foaming plastic is characterized in that:
The ratio of each component is following:
The A component: 4,10 parts of the two glycol phthalates of 4-oxygen;
The B component: polyether glycol SC-450, hydroxyl value is 450mgKOH/g, 390 parts;
The C component: 3 parts of triethylene diamine catalyzer, 3 parts of B8433 silicon foams stablizers, 1,15 parts of 1-two chloro-1-fluoroethane (F141b) whipping agents are as 2 parts in the water of whipping agent, 15 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 105 parts of poly methylene poly phenyl poly isocyanates;
As 4 of A component, the structural formula and the preparation method of the two glycol phthalates of 4-oxygen are following:
Weigh 4, the two Tetra hydro Phthalic anhydrides of 4-oxygen, terepthaloyl moietie, mol ratio is 1: 20, joins in the reaction kettle that TM and condensing surface are housed, 120 ℃ of heated and stirred are even; Be cooled to room temperature, add the strongly acidic cationic exchange resin CT275 as catalyzer, add-on is 4,2% mass ratio of the two Tetra hydro Phthalic anhydrides of 4-oxygen; Stir down and be warming up to 185 ℃ gradually, keep this temperature and refluxed 10 hours, reduced to 2 o'clock to the acid number of reaction system, GB1668-8 stirs down temperature of reaction kettle is reduced to room temperature; Emit material in the still, the solids removed by filtration catalyzer; Than aqueous sodium hydroxide solution agitator treating, isolate behind the product with 5% quality of 2 volumes times again and wash than aqueous sodium carbonate by standing demix with 4 volumes, 5% quality doubly for the reaction mass of gained; Standing demix adds isolating product and is equipped with in the still kettle of TM and condensing surface, is 0.1MPa in 150 ℃, decompression, vacuum tightness, steams except that residual terepthaloyl moietie to cut to steam, and is cooled to 50 ℃; In 50 ℃, the gac that in the material of gained, adds inventory 1% mass ratio stirs after 1 hour and cools the temperature to room temperature; Discharging removes by filter gac, obtains 4 of purifying, the two glycol phthalates of 4-oxygen, and yield 85%, purity are 98%;
The preparation method of said high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 10 parts of A components and 90 parts of B component uniform mixing;
2), 17 parts of whipping agents, 3 parts of catalyzer, 3 parts of suds-stabilizing agents and 15 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds the polyvalent alcohol storage tank of polyurethane foaming machine, in the A storage tank, poly methylene poly phenyl poly isocyanate joined the isocyanic ester storage tank of polyurethane foaming machine, in the B storage tank;
4), at a high speed, greater than 6000 rev/mins of uniform mixing with the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank; Be poured into then in the irony mould;
5), question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
2. high compression-strength rigid-enhancement type hard polyurethane foaming plastic is characterized in that:
The ratio of each component is following:
The A component: 4,20 parts of the two glycol phthalates of 4-oxygen;
The B component: polyether glycol ST-480, hydroxyl value is 480mgKOH/g, 40 parts; Polyether glycol PN-560, hydroxyl value is 560mgKOH/g, 35 parts; Polyether glycol TD-400, hydroxyl value is 400mgKOH/g, 5 parts;
The C component: 2 parts of triethylene diamine catalyzer, 2.5 parts of AK-8802 silicon foams stablizers, 9 parts of F141b whipping agents are as 2 parts in the water of whipping agent, 15 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 105 parts of poly methylene poly phenyl poly isocyanates;
The preparation method of said high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 20 parts of A components and 80 parts of B component uniform mixing;
2), 11 parts of whipping agents, 2 parts of catalyzer, 2.5 parts of suds-stabilizing agents and 15 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds the polyvalent alcohol storage tank of polyurethane foaming machine, in the A storage tank, poly methylene poly phenyl poly isocyanate joined the isocyanic ester storage tank of polyurethane foaming machine, in the B storage tank;
4), at a high speed, greater than 6000 rev/mins of uniform mixing with the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
3. high compression-strength rigid-enhancement type hard polyurethane foaming plastic is characterized in that:
The ratio of each component is following:
The A component: 4,15 parts of the two glycol phthalates of 4-oxygen;
The B component: polyether glycol 4110, hydroxyl value are 400mgKOH/g, 20 parts; Polyether glycol ST-481, hydroxyl value is 481mgKOH/g, 40 parts; Polyester polyol PS-3152, hydroxyl value is 315mgKOH/g, 15 parts;
C component: 2 parts of triethylene diamine catalyzer, 2 parts of B8433 silicon foams stablizers, 2 parts in water, 12 parts of four (2-chloroethyl) diethylidene ether bis-phosphate flame retardants;
D component: 102 parts of poly methylene poly phenyl poly isocyanates;
According to the above ratio A component and B component are mixed, add the C component and mix, inject the A storage tank of foaming machine; Poly methylene poly phenyl poly isocyanate is injected foaming machine B storage tank; According to the above ratio, the material in the A, B storage tank is through at a high speed, after mixing greater than 6000 rev/mins, is poured in the irony mould; After question response finishes, i.e. after foam curing is also cooled off naturally fully, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, obtain high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
4. high compression-strength rigid-enhancement type hard polyurethane foaming plastic is characterized in that:
The ratio of each component:
The A component: 4,15 parts of the two phthalic acid one condensed ethandiol esters of 4-oxygen;
The B component: polyether glycol GNE410, hydroxyl value is 410mgKOH/g, 40 parts; Polyether glycol PN-560, hydroxyl value is 560mgKOH/g, 45 parts;
C component: 1.5 parts of catalyzer triethylenediamines, 2.5 parts of B8466 silicon foams stablizers, 15 parts of whipping agent pentanes, 12 parts of dimethyl methyl phosphonate (DMMP) fire retardants;
D component: 104 parts of poly methylene poly phenyl poly isocyanates;
Said as 4 of A component, the structural formula and the preparation method of the two phthalic acid one condensed ethandiol esters of 4-oxygen are following:
Weigh 4, the two Tetra hydro Phthalic anhydrides of 4-oxygen, a condensed ethandiol, mol ratio is 1: 20, joins in the reaction kettle that TM and condensing surface are housed, 120 ℃ of heated and stirred are even; Be cooled to room temperature, add the strongly acidic cationic exchange resin CT275 as catalyzer, add-on is 4,2% mass ratio of the two Tetra hydro Phthalic anhydrides of 4-oxygen; Stir down and be warming up to 185 ℃ gradually, keep this temperature and refluxed 10 hours, reduced to 2 o'clock to the acid number of reaction system, GB1668-8 stirs down temperature of reaction kettle is reduced to room temperature; Emit material in the still, the solids removed by filtration catalyzer; Than aqueous sodium hydroxide solution agitator treating, isolate behind the product with 5% quality of 2 volumes times again and wash than aqueous sodium carbonate by standing demix with 4 volumes, 5% quality doubly for reaction mass; Standing demix is equipped with isolating product adding in the still kettle of TM and condensing surface, in 180 ℃, and decompression, vacuum tightness is 0.05MPa, steaming removes a residual condensed ethandiol to cut and steams, and is cooled to 50 ℃; In 50 ℃, the gac that in the material of gained, adds inventory 1% mass ratio stirs after 1 hour and cools the temperature to room temperature; Discharging removes by filter gac, obtains 4 of purifying, the two phthalic acid one condensed ethandiol esters of 4-oxygen, and yield 80%, purity are 97.8%;
The preparation method of said high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 15 parts of A components and 85 parts of B component uniform mixing;
2), 15 parts of whipping agents, 1.5 parts of catalyzer, 2.5 parts of suds-stabilizing agents and 12 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds the polyvalent alcohol storage tank of polyurethane foaming machine, in the A storage tank, poly methylene poly phenyl poly isocyanate joined the isocyanic ester storage tank of polyurethane foaming machine, in the B storage tank;
4), at a high speed, greater than 6000 rev/mins of uniform mixing with the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 3 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
5. high compression-strength rigid-enhancement type hard polyurethane foaming plastic is characterized in that:
The ratio of each component is following:
The A component: 4,18 parts of the two phthalic acid one condensed ethandiol esters of 4-oxygen;
The B component: polyether glycol GNE410, hydroxyl value is 410mgKOH/g, 50 parts; Polyester polyol PS-3152, hydroxyl value is 315mgKOH/g, 32 parts;
C component: 1.5 parts in two (2-dimethylaminoethyl) ether, 3 parts of B8469 silicon foams stablizers, 10 parts of pentanes, 12 parts of four (2-chloroethyl) diethylidene ether bisphosphates;
D component: 105 parts of poly methylene poly phenyl poly isocyanates;
The preparation method of said high compression-strength rigid-enhancement type hard polyurethane foaming plastic is following:
1), with 18 parts of A components and 82 parts of B component uniform mixing;
2), 10 parts of whipping agents, 1.5 parts of catalyzer, 3 parts of suds-stabilizing agents and 12 parts of fire retardants are joined in the mixture of step 1) gained, mix;
3), with step 2) mixture of gained adds the polyvalent alcohol storage tank of polyurethane foaming machine, in the A storage tank, poly methylene poly phenyl poly isocyanate joined the isocyanic ester storage tank of polyurethane foaming machine, in the B storage tank;
4), at a high speed, greater than 6000 rev/mins of uniform mixing with the poly methylene poly phenyl poly isocyanate in mixture in the A storage tank and the B storage tank; Be poured into then in the irony mould;
5), after question response finishes, after promptly the foam in the irony mould solidifies and cools off fully naturally, the demoulding, the room temperature held cuts epidermis on cutting machine after 5 days, promptly get high compression-strength rigid-enhancement type hard polyurethane foaming plastic.
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