CN1528801A - Method for preparing perfomed polymer for monocomponent polyurethane foam gule - Google Patents
Method for preparing perfomed polymer for monocomponent polyurethane foam gule Download PDFInfo
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Abstract
The invention is a prepolymer for monocomponent polyurethane foam sealing gum, making the mixture of polyether or polyester polyalcohol which has molecular weight 400-3000 and functionality 2-5 and contains ethylene oxide (EO) structural unit (-CH2-CH2-O-) 100 shares, oxane-propylene oxide copolyether modified siloxane foam stabilizer 0.5-3 shares (weight share); morpholine catalyst 0.1-1 share (weight share), phosphorous flame retardant 10-100 shares (weight share), and polyisocyanate whose weight exceeds the polyalcohol hydroxy equivalent weight by 2-7 times (namely 'rough MDI'), etc., to react at 30-80 deg.C for 2 hours so as to prepare the prepolymer, its NCO content 5-16%, and its viscosity increase not greater than 10% after stored for one year, and the foam prepared of it has volume density 19-28Kg/cu m, heat conductivity coefficient 30-55W/m.K, closed cell rate 65-80% and flame retardant rating B2 or B3.
Description
(1) technical field
The present invention relates to a kind of preparation method of performed polymer, relate to the preparation method of a kind of moisture-curable one-component polyurethane foam tackiness agent or rather with performed polymer.
(2) background technology
The polyurethane foam seal gum has good thermal insulation, low water absorption, bonding elasticity and lower temperature resistance.Be suitable for the required sealing and plugging of multiple material of construction, insulation insulation, filling perforation are squeegeeed, fixed bonding.Especially be fit to the occasions such as sealing, waterproof and sound insulation between air-conditioning pipe and body of wall and plastic-steel, steel or aluminum alloy doors and windows and body of wall.The foam glue that also has this moisture-curable has special advantages aspect porous material and sheet material (as aluminium sheet, steel plate or BMC plate etc.) compound.Because purposes enlarges day by day, promote research and development to its preparation method.
The polyurethane foam seal gum has two-pack and single component two major types, and the two-pack preparation method often is made up of A component and B component.The A component comprises: organic polyhydric alcohol, catalyzer, whipping agent and additive, the B component is made of polyisocyanates and some possible auxiliary agents, A, B component store separately at a pair of chamber container during can, allow A, B two components mix rapidly during use, form quick-setting foaming mixtures, do not need moisture to participate in also carrying out foam seal.The advantage of this method is that storage period is long.The two chambers cost of container that has mixed structure that shortcoming is to store A, B component is expensive, and A, B mixture must once use up in case mix simultaneously.
The single-component preparation method claims an one step preparation method again.This method will contain polyisocyanates or modified polyisocyanate and polyvalent alcohol, whipping agent, catalyzer and other auxiliary or additive by metering, be added in the mixing equipment in the lump with independent or form of mixtures, mix and topple over by mixing die head, enter storage tank via partitioning device.
Prior art U.S.Pat.No 4,258,140th, and single-component prepares the method for performed polymer.Polyurethane foam is 40～500 by the mixture of diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates (being called " thick MDI ") with hydroxyl value with performed polymer, and molecular weight is the polyol reaction preparation that contains the chemical bonding tertiary amine groups on 500～5000 trifunctional or four functional polyester polyvalent alcohols or polyether glycol and the main chain.Then under pressure, contain the performed polymer of isocyanate groups and whipping agent and supplementary additive and from pressurized vessel, emit and the stable polyurethane foam of air effect preparation size.Be longer than 60 ℃ storage time with the performed polymer of this technology preparation and can store 60 days at least.Can store 18 months in room temperature.Foaming properties after the performed polymer foaming is density 20～35Kg/m
3, sample after rate is 5～10%, 2～3 hours time of coagulation, 5～8 hours set times.
Without catalyzer, the characteristics of this method were to have overcome to solidify slow shortcoming, eliminate the after phenomenon, solve the problem on deformation of foam-filled goods when prior art was used polyvalent alcohol with polyol blends that contains the tertiary amine structure and polyisocyanates prepared in reaction performed polymer.Foam size stability is good relatively, but stability in storage is still undesirable, and foaming density obviously becomes big phenomenon along with the prolongation in storage time when practical application, and density can be increased to more than 2 times or 2 times after storing 6 months.
(3), summary of the invention
In order to improve the deficiencies in the prior art part, the preparation shelf lives is long, and curing speed is fast, foam article dimensional stability, even, the without issue intumescent performed polymer of abscess.For this reason, complete design of the present invention is proposed.
One-component polyurethane foam tackiness agent performed polymer of the present invention is to be 400～3000 by molecular weight, functionality be 2～5 contain ethylene oxide (EO) structural unit (CH
2-CH
2-O-) polyethers or 100 parts of polyester polyols, 0.5～3 part of foam stabilizer of epoxy ethane-epoxy propane copolyether modified siloxane (weight part); Morpholine class catalyzer 0.1～1 part of (weight part), 10～50 parts (weight parts) of phosphonium flame retardant and polyisocyanates (i.e. " thick MDI ") more excessive 2～7 times than polyvalent alcohol hydroxyl equivalent are formed;
Here, " thick MDI " accounts for 35～65% (weight parts) of the whole pre-scale of construction.Polyether glycol or the pure and mild phosphonium flame retardant of polyester polyols etc. are at 60～120 ℃, and dehydration is 2 hours under 32～665Pa condition, is cooled to normal temperature, and logical nitrogen adds " thick MDI " then to normal pressure, and at 30～80 ℃, nitrogen atmosphere reaction was down made performed polymer in 2 hours.Then performed polymer and whipping agent are filled into respectively in the pressurized vessel for using.Perhaps add the performed polymer that an amount of volatile solvent is modulated into certain viscosity to performed polymer.Also can in system, add functional aid such as rodenticide, sterilant and mould inhibitor or the like, to satisfy the needs of different occasions.
Morpholine class catalyzer can be chosen a class wantonly from N-alkyl morpholine, N-alkoxyalkyl morpholine, N-hydroxyalkyl morpholine, two [N-alkyl (alkyl morpholine)] ether, representational as N-ethylmorpholine, N-hydroxyethyl morpholine, N-(methoxy ethyl) morpholine, two (N-ethylmorpholine) ether (BMDEE) etc., preferably select N-hydroxyethyl morpholine and two (N-ethylmorpholine) ether etc. for use.
Phosphonium flame retardant can be from dimethyl methyl phosphonate (DMMP), three (2-chloroethyl) phosphoric acid ester (TCEP), three (chloropropyl) phosphoric acid ester (TCPP), three (2,3-two chloropropyls) phosphoric acid ester (TDCPP), (2,3-two chloropropyls) two (2-chloropropyl) phosphoric acid ester, (2-chloropropyl) two (2,3-two chloropropyls) phosphoric acid ester, choose any one kind of them in three (2, the 3-dibromopropyl) phosphoric acid ester (TDBPP) triphenylphosphate, the triphenyl phosphite or their mixture.
" thick MDI " is the mixture of polyphenyl polymethylene polyisocyanates and diphenylmethanediisocyanate (MDI), steps Rubinate 5005,5025 of (Huntsman) company or the like as the 44V20 of Bayer (Bayer) company, the MR-200 of Japanese polyurethane (NPU) company, the M20S and the Hensel of BASF (BASF) company.
The described ethylene oxide structural unit (CH that contains of performed polymer preparation method
2-CH
2-O-) polyethers or polyester polyol can be polyether glycol, polyester polyol or their mixture.This polyvalent alcohol or their mixture contain 5～30% ethylene oxide structural unit (CH
2-CH
2-O-).If what adopt is the mixture of polyvalent alcohol, this means that the some of them polyvalent alcohol can not contain ethylene oxide structural unit (CH
2-CH
2-O-), but have at least a kind of polyvalent alcohol to contain the ethylene oxide structural unit (CH of some amount
2-CH
2-O-).Employing contains the formed performed polymer of polyvalent alcohol of ethylene oxide structural unit, when forming porous foam, can absorb moisture, promote foamy to solidify, thereby can significantly reduce morpholine class catalyst consumption, improve the stability of performed polymer, correspondingly improve the storage period of goods, improve the foamy dimensional stability, if the ethylene oxide structural unit (CH of used polyvalent alcohol
2-CH
2-O-) content then causes moisture absorption insufficient less than 5% easily, and the foamy dimensional stability is descended; Otherwise, if content above 30%, then causes foam hardness to decline to a great extent and the decline of antiseepage water-based.
Described polyether glycol is a propylene oxide terminated polyether polyvalent alcohol, promptly end is the polyether glycol of secondary hydroxyl, this polyvalent alcohol not only can reduce the speed with " thick MDI " prepolymerization reaction, and formed performed polymer has stability preferably, has better manufacturability simultaneously.
Described polyester polyol is to be the polyester glycol that main dibasic alcohol and hexanodioic acid, phthalic anhydride, terephthalic acid, m-phthalic acid or dimethyl terephthalate (DMT) (DMT) etc. prepare through condensation reaction by ethylene glycol (EG), glycol ether (DEG) or Triethylene glycol (TEG).But in small molecules glycol, can add 1 based on EG, DEG or TEG, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol are participated in condensation reaction and are prepared polyester glycol; Also can add 1,1,1-TriMethylolPropane(TMP) (TMP), 2,2-dimethylol propionic acid (DMPA) or Viscotrol C prepare functionality at 2.01～2.50 polyester polyol.
The described whipping agent of preparation method can be from 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-three fluoro-2-fluoroethanes (HFC-134a), 1, optional two kinds or their mixture in 1-two fluoro-2-fluoroethanes (HCFC-22), Trimethylmethane (A-31), dme, third butane (A-46) etc.Can be as the frothing aid that the porous material tackiness agent is used from acetone, methylene dichloride, 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1,1,3,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3, choose any one kind of them in 3-3-pentafluorobutane (HFC-365mfc), the pentamethylene etc. or their mixture.
The described sterilant of preparation method can be selected from pyrethroid and nontoxic arsenide, chooses any one kind of them or their mixture as permethrin, Deltamethrin, Cypermethrin, cyfloxylate or the like.
The polyurethane foam seal gum of the present invention preparation with the construction property of performed polymer for not gluing the time: about 8～10 minutes (20 ℃, relative humidity 60%), the completely solidified time: 12～24 hours, (2.5 centimetres wide for expansion ratio 40～66,20 ℃, relative humidity 60%).Foam characteristic is: volume density is 19～28%Kg/m
3Foam characteristic: volume density, thermal conductivity 30～55mW/m.k, rate of closed hole 65～80%, flame retardant rating B
2Or B
3
(4) embodiment
Especially exemplified by example it is described in order to implement the present invention better, but is not limitation of the present invention.
Example 1
The 284g molecular weight is 2000 the end capped epoxy ethane-epoxy propane copolyether of propylene oxide polyvalent alcohol (OHV84.1), the 76g molecular weight dehydration that is 1000 propylene oxide polyether glycol (OHV112.2) and 104g three (2-chloroethyl) phosphoric acid ester (TCEP) under 70～400 ℃, the condition of 32～665Pa pressure 2 hours, be cooled to normal temperature, logical nitrogen to normal pressure, add the siloxanes foam stabilizer of 4g N-ethylmorpholine, the modification of 12g epoxy ethane-epoxy propane copolyether and 320g " thick MDI " then, reaction became performed polymer in 2 hours under 40～70 ℃, nitrogen atmosphere.Then with performed polymer and whipping agent 1,1-C2H4F2 C2H4F2 (HFC-152a) and Trimethylmethane canned go in the pressurized vessel seal usefulness for foaming.Isocyanate group in the base polyurethane prepolymer for use as (NCO content)=12.5%, viscosity are 10500cPs (25 ℃), store viscosity increase in 12 months and are no more than 5%.Foaming properties is volume density 25Kg/m
3, thermal conductivity 36mW/m.k, rate of closed hole 71%, flame retardant rating are B
3
Example 2
The 195g molecular weight is 3000 the end capped epoxy ethane-epoxy propane copolyether of propylene oxide polyvalent alcohol (OHV56.1, EO=30%), the 140g molecular weight is 600 propylene oxide polyether glycol (OHV187), the 33g molecular weight be 600 be the propylene oxide polyether glycol and the 160g (2-chloropropyl) two (2 of initiator with the quadrol, 3-two chloropropyls) phosphoric acid ester is at 120 ℃, 532～665Pa pressure condition dewatered 2 hours down, be cooled to normal temperature, logical nitrogen is to normal pressure, add 2g N-hydroxyethyl morpholine then, 25g siloxanes-epoxy propane copolymer and 602g " thick MDI ", at 40～70 ℃, nitrogen atmosphere reaction was down made performed polymer in 2 hours, the isocyanate group content (NCO)=14.0% of gained base polyurethane prepolymer for use as, then with this performed polymer of 650g and 100g 1,1,1-three fluoro-2-fluoroethanes (HFC-134a) and 60g dme are filled in the aerosol jar that has the gun-type valve door.As a result, store viscosity increase in a year and be no more than 9%, foaming properties is apparent density 22Kg/m
3, thermal conductivity 45mW/m.k, rate of closed hole 70%.
Example 3: in the performed polymer of example 2 gained, get 650g, add 9.5 Deltamethrines and 100g 1,1,1-three fluoro-2-fluoroethanes (HFC-134a) and 60g dme are filled in the aerosol jar that has the gun-type valve door.As a result, the foam of gained has the function of termite extremely, and foaming properties is apparent density 22Kg/m
3, thermal conductivity 46mW/m.k, rate of closed hole 70%.
Example 4
The 120g molecular weight is 1000 epoxy ethane-epoxy propane copolyether polyvalent alcohol (OHV168.2, EO=12%), the 100g molecular weight is 1000 epoxy ethane-epoxy propane copolyether polyvalent alcohol (OHV112, EO=10%) and 63g tricresyl phosphate (2,3-dichloro propyl diester) (TDCPP) under 532～665P pressure, dewatered 2 hours in 65 ℃, cool to room temperature, logical nitrogen is to normal pressure, add two (N-ethylmorpholine) ethers of 2.1g and 320g " thick MDI " then, made performed polymer in 2 hours 30～80 ℃ of reactions.Gained performed polymer isocyanic ester (NCO) content=12.2% stores viscosity increase in a year and is no more than 5%.
Get the above-mentioned performed polymer of 200g 30g 1,1-two chloro-1-fluoroethanes (HCFC-141b) dilute.The compoiste adhering that can be used for porous medium such as hard polyurethane foam and steel plate, unsaturated polyester (BMC) sheet material and aluminium sheet.
Example 5
Except that adding the 100g molecular weight is that 600 polyester polyols (this polyvalent alcohol is that a condensed ethandiol, dimethyl terephthalate (DMT) (DMT) prepare gained by 1.1: 1 molar reactives), 120g molecular weight are 1000 propylene oxide polyether glycol (OHV168), 400g " slightly MDI ", 2g N-ethylmorpholine, the 80g triphenylphosphate, other operations are with example 1 sample, isocyanate group content is 13.5% as a result, stores viscosity increase in a year and is no more than 6%.Foaming properties is volume density 27Kg/m
3, thermal conductivity 34mW/m.k rate of closed hole 77%.
Claims (9)
1, a kind of one-component polyurethane foam tackiness agent is with the preparation method of performed polymer, and it is characterized in that: by molecular weight is 400～3000, functionality be 2～5 contain ethylene oxide structural unit (CH
2-CH
2-polyethers O-) or siloxanes foam stabilizer 1～6 weight part of polyester polyol 100 weight parts, the modification of epoxy ethane-epoxy propane copolyether; Morpholine class catalyzer 0.3～3 weight part, phosphonium flame retardant 5～100 weight parts and the polyisocyanates more excessive 2～7 times than polyvalent alcohol hydroxyl equivalent are formed;
Polyethers or polyester polyol, the siloxanes foam stabilizer, morpholine class catalyzer and phosphonium flame retardant are at 60～120 ℃, dehydration was cooled to normal temperature in 2 hours under the condition of 532～662Pa, logical nitrogen is to normal pressure, then with polyisocyanates, at 30～80 ℃, performed polymer was made in reaction in 2 hours under the atmosphere of nitrogen, then performed polymer can be packed into together with aerosol propellant and make the monocomponent bubble seal gum of moisture-curable in the pressurized vessel, perhaps add an amount of volatile solvent and be deployed into the performed polymer of certain viscosity, as the tackiness agent of porous material, also can in system, add functional aid such as rodenticide, sterilant and mould inhibitor.
2, performed polymer preparation method according to claim 1 is characterized in that: the described ethylene oxide structural unit (CH that contains
2-CH
2-O-) polyethers or polyester polyol can be polyether glycol, polyester polyol or their mixture, and this polyvalent alcohol or their mixture contain the ethylene oxide structural unit (CH of 5～30% weight parts
2-CH
2-O-).
3, according to the described performed polymer preparation method of claim 1, it is characterized in that: the described ethylene oxide structural unit (CH that contains
2-CH
2-O-) polyvalent alcohol or polyol blends, used polyether glycol is a propylene oxide terminated polyether polyvalent alcohol, promptly end is the polyether glycol of secondary hydroxyl.
4, performed polymer preparation method according to claim 1 is characterized in that: described polyester polyol is to be the polyester glycol that main dibasic alcohol and hexanodioic acid, phthalic anhydride, terephthalic acid, m-phthalic acid or dimethyl terephthalate (DMT) prepare through condensation reaction by ethylene glycol EG, glycol ether DEG or Triethylene glycol TEG.In the small molecules glycol based on EG, DEG or TEG, can add 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol are participated in condensation reaction and are prepared polyester glycol; Also can add 1,1,1-TriMethylolPropane(TMP) (TMP), 2,2-dimethylol propionic acid (DMPA) or Viscotrol C prepare functionality at 2.01～2.50 polyester polyol.
5, performed polymer preparation method according to claim 1, it is characterized in that: described morpholine class catalyzer, can from N-alkyl morpholine, N-alkoxyalkyl morpholine, N-hydroxyalkyl morpholine, two [N-alkyl (alkyl morpholine)] ether, choose a class wantonly, representational as N-ethylmorpholine, N-hydroxyethyl morpholine, N-(methoxy ethyl) morpholine, two (N-ethylmorpholine) ether (DMDEE).
6, performed polymer preparation method according to claim 1, it is characterized in that: described phosphonium flame retardant can be from dimethyl methyl phosphonate (DMMP), three (2-chloroethyl) phosphoric acid ester (TCEP), three (chloropropyl) phosphoric acid ester (TCPP), three (2,3-two chloropropyls) phosphoric acid ester (TDCPP), (2,3-two chloropropyls) two (2-chloropropyl) phosphoric acid ester, (2-chloropropyl) two (2,3-two chloropropyls) choose any one kind of them in phosphoric acid ester, three (2, the 3-dibromopropyl) phosphoric acid ester (TDBPP), triphenylphosphate, the triphenyl phosphite or their mixture.
7, performed polymer preparation method according to claim 1 is characterized in that, described polyisocyanates is the mixture of polyphenyl polymethylene polyisocyanates (PAPI) and diphenylmethanediisocyanate (MDI), promptly so-called " thick MDI ".
8, performed polymer preparation method according to claim 1, it is characterized in that: the whipping agent in the described foam seal glue can be from 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-three fluoro-2-fluoroethanes (HFC-134a), 1, optional two kinds or their mixture in 1-two fluoro-2-fluoroethanes (HCFC-22), Trimethylmethane (A-31), dme, third butane (A-46) etc.; Frothing aid in the described porous material tackiness agent can be from acetone, methylene dichloride, 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1,1,3,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3, choose any one kind of them in 3-3-pentafluorobutane (HFC-365mfc), the pentamethylene or their mixture.
9, performed polymer preparation method according to claim 1 is characterized in that: described sterilant can be selected from pyrethroid and nontoxic arsenide, as permethrin, Deltamethrin, Cypermethrin, cyfloxylate.
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