CN1683425A - Polymer polyester polyol, its producing process and its use - Google Patents
Polymer polyester polyol, its producing process and its use Download PDFInfo
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- CN1683425A CN1683425A CN 200510042466 CN200510042466A CN1683425A CN 1683425 A CN1683425 A CN 1683425A CN 200510042466 CN200510042466 CN 200510042466 CN 200510042466 A CN200510042466 A CN 200510042466A CN 1683425 A CN1683425 A CN 1683425A
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Abstract
The present invention features that the polymer with polyester polyol is prepared through the in-situ polymerization of ethylene monomer in basic polyester polyol to form the dispersed phase in the presence of dispersant and other assistants. The polymer has polyethylene as the dispersed phase and the polyester polyol as the continuous phase, and has low viscosity, high storing stability, adjustable foam density and structure, improved size stability, raised product performance and low cost.
Description
(1) technical field:
The present invention relates to a kind of polymer polyester polyol, its production technique and application thereof, belong to industrial chemicals production and applied technical field.
(2) technical background:
As everyone knows, polyurethane products such as flexible PU foam and micro-pore elastomer are because it has characteristics such as excellent load, resistance to tearing, fabulous rebound resilience and comfortableness, being applied in the daily life more and more widely.Adopted different measures in order further to improve the product properties or the people that reduce cost.First kind method is added mineral filler exactly in raw material, to improve the mechanical property of goods, reduce cost, but mineral filler is bigger owing to having particle, there are not characteristics such as chemical action with external phase, the shelf-stable performance of raw material is poor on the one hand, though there is the people to adopt chemical process that filler is handled, stabilising effect still is undesirable; On the other hand, limited although mineral filler can reduce cost to the modified effect of material, even destroy bigger to some performance.Second class methods are carried out modification to raw material exactly, material modification comprises to the modification of isocyanate products with to the modification of polyvalent alcohol product, modification to isocyanate products does not add detailed description here, modification to the polyvalent alcohol product is exactly nothing but to select special material or add polymkeric substance, wherein, introducing the polymer manufacture polymer polyatomic alcohol is a kind of effective way.
Polymer polyatomic alcohol and the purposes in polyurethane products thereof are well-known, it is to be filled in the mixture system that forms in the polyvalent alcohol with the polymkeric substance of thiazolinyl unsaturated monomer or multipolymer, be to form by the dispersion polymerization of alkenyl monomer in polyvalent alcohol, as CN1067059A and CN1160061C (96112759.7), adopting vinyl cyanide and vinylbenzene and so on monomer is polymeric matrix, introduce the ethers macromonomer, form graftomer by vinyl monomer grafting on the ether active site and play the polymer polyatomic alcohol that the dispersion agent effect prepares.This polyvalent alcohol is used for flexible PU foam can provide good perforate performance, improves hardness and supporting capacity.
It is the preparation method of the polymer polyatomic alcohol of polymerization single polymerization monomer that US4503207 has described with vinyl cyanide and methyl methacrylate.
On the basis of US4454255 and the former patent of US4458038, adopt polyethers-cis-butenedioic anhydride-ethylene oxide type dispersion agent, made high solids content, low viscosity polymer polyvalent alcohol, and be successfully applied to soft bubble and elastomerics.
But more than preparing the polyvalent alcohol that is adopted in the method for polymer polyatomic alcohol all is polyethers, and this just makes the Application Areas of polymer polyatomic alcohol be restricted.On the one hand,, it is restricted in some Application for Field because the characteristics of polyethers itself have determined that its mechanical property is relatively poor, such as, the field just has 85% to adopt the polyester system at the bottom of the polyurethane shoe at present.On the other hand, if with polymer polyatomic alcohol as adding modified product, because the polarity of polyester and polyethers and activity difference cause occurring easily in the raw material storage process being separated, reaction process is not easy control, therefore be not suitable for the polyester system so yet.
It is the processing method of external phase synthesis of polymer polyalcohol that US5830944 has described with the polyester, but the dispersion agent that it adopts is the isocyanate group macromonomer.
It is the method for dispersion agent synthetic polymer polyester that EP0250351 has described a unsaturated macromers, but its synthetic dispersion agent dispersion efficiency is low, and dispersant dosage is big; In polymer polyester synthetic, do not use chain-transfer agent.
(3) summary of the invention: the object of the invention is to overcome the deficiency of above-mentioned prior art and polymer polyatomic alcohol that a kind of polyester system is provided, the dispersion agent that it adopts, polymer polyester all there is good dispersion effect, resulting polymer polyester polyol product shelf-stable, modest viscosity, this polymer polyester polyol is used for elastomerics fields such as the soft bubble of polyester system, sole and can plays significant modification and fall close effect, improved load, the dimensional stability of low density goods greatly.
Content of the present invention can reach by following measure: a kind of polymer polyester polyol, it is characterized in that in the presence of dispersion agent and other auxiliary agent, vinyl monomer generates by in-situ polymerization in the base polyester polyvalent alcohol, this polymer polyester polyol is an external phase with the base polyester, is disperse phase with the polymer beads.When needs are regulated molecular weight, also can use molecular weight regulator.
In order further to realize purpose of the present invention, the functionality of described base polyester polyvalent alcohol is in the 2-5 scope, and molecular weight is at 500-3000, and acid number is less than 5mgKOH/g.
In order to realize that further purpose of the present invention, described base polyester polyvalent alcohol are a kind of or any several mixture in hexanodioic acid kind polyester polyvalent alcohol, Tetra hydro Phthalic anhydride (terephthalic acid) the kind polyester polyvalent alcohol.Hexanodioic acid kind polyester polyvalent alcohol be hexanodioic acid-glycols, hexanodioic acid-Diethylene Glycol class, hexanodioic acid-1.4 butyleneglycol class, hexanodioic acid-ethylene glycol-glycol ether class, hexanodioic acid-ethylene glycol-butyleneglycol class, hexanodioic acid-glycol ether-butyleneglycol class or hexanodioic acid with the composite productions of different small molecular alcohols such as glycol ether, glycerine, neopentyl glycol polyester polyol in a kind of or several mixture arbitrarily; Tetra hydro Phthalic anhydride (terephthalic acid) kind polyester polyvalent alcohol is phthalic anhydride-glycol ether class, phthalic anhydride-glycols, phthalic anhydride-glycerols or with phthalic anhydride and several different small molecular alcohols such as glycol ether, glycerine a kind of in the composite aromatics polyester polyol that makes or several mixture arbitrarily arbitrarily; Vinyl monomer is a kind of in vinylbenzene, vinyl cyanide, divinyl, vinyl toluene, ethyl styrene, vinylformic acid, acrylate, the methyl methacrylate or composite arbitrarily between them.
In order further to realize purpose of the present invention, described auxiliary agent is the free radical reaction initiator, be isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate, a kind of in the persulphate or composite arbitrarily between them.
In order further to realize purpose of the present invention, described auxiliary agent is a kind of in methyl alcohol, Virahol, butanone, iodoform, iodine, lauryl mercaptan, preferred butanone, the lauryl mercaptan or composite arbitrarily between them for the chain-transfer agent chain-transfer agent.
In order further to realize purpose of the present invention, described dispersion agent is a kind of parents' macromonomer, its consumption is 2%-10%, the preparation method of macromonomer can adopt diverse ways to synthesize according to the kind of used base polyester and the kind of used vinyl monomer, the synthetic principle is the characteristic that the existing and used base polyester of the macromonomer that obtains is mixed, again can be well and polymer graft become one.It can make by base polyester and the monomer reaction that contains unsaturated link(age).
In order further to realize purpose of the present invention containing unsaturated acid in the described dispersion agent, be fumaric acid, MALEIC ANHYDRIDE or composite arbitrarily between them, preferred fumaric acid.
Dispersion agent can prepare with following method:
Method one: the polyester macromolecule with molecular weight 1000-4000 reacts with the fumaric acid that is equivalent to polyester 0.5-2.0 times mole number at 100-150 ℃, after reacting completely, at 100-120 ℃ with ethylene oxide-capped, after end capping is complete, under 0.07-0.09MPa vacuum tightness, reduce pressure, make after removing free oxyethane.
Method two: under the esterifying catalyst effect, with the polyester macromolecule of molecular weight 1000-4000 200 ℃ down with the fumaric acid or the maleic acid anhydride reactants of 0.5-2.0 times of polyester macromolecule mole number, add glycol ether afterwards, reduce to 3.0mgKOH/g when acid number and make when following.
Method three: under the esterifying catalyst effect, react with the following fumaric acid of the polyester macromolecule of molecular weight 1000-4000 with 0.5-2.0 times of polyester macromolecule mole number at 200 ℃, when acid number is reduced to 3.0mgKOH/g when following, be cooled to 100-130 ℃, add the vinyl monomer that is equivalent to macromonomer mass fraction 30%-70% and be equivalent to macromonomer molfraction 0.5-1.2 initiator doubly, react after 1-4 hour, be decompressed to vacuum tightness 0.07-0.09MPa, remove unreacted monomer and make.
Described catalyst for esterification reaction is titanium, tin and antimony class catalyzer.Be a kind of in two lauric acid diisobutyl tin, tetrabutyl titanate and antimonous oxide, the tetrabutyl titanate or composite arbitrarily between them.
Described catalyst concentration scope is at 30-300ppm, and preferable range is at 50-100ppm.
In order further to realize purpose of the present invention, the particle size range 50-500nm of described polymer beads; Molecular weight is at 6000-15000; Content in polymer polyester polyol is at 5%-30%.
In order further to realize purpose of the present invention, described polymer polyester polyol is a kind of oyster white thick liquid, acid number is less than 3.0mgKOH/g, preferably less than 1.0mgKOH/g, hydroxyl value is decided according to the base polyester hydroxyl value, can reduce 5%-30% on the basis of base polyester hydroxyl value, viscosity is at 1500-6000mPa.s (40 ℃), preferred 2000-4000mPa.s, package stability is in 3 months to 18 months scopes, and preferred 8-12 month polymer beads stable existence is in the external phase polyester.
A kind of production technique of polymer polyester polyol, comprise that raw material mixes and synthetic two stages of polymkeric substance, mix stages at raw material, with vinyl monomer, initiator, chain-transfer agent metered charge, mix low temperature and place, in order to prevent decomposition of initiator, storage period can not be long, temperature can not be too high, is preferably under the normal temperature within one day to use.Synthesis phase at polymkeric substance; the above gob for preparing is added in the base polyester polyvalent alcohol that contains dispersion agent; concrete grammar is as follows: base polyester polyvalent alcohol, dispersion agent and part of auxiliary are joined in the reactor; under nitrogen protection, be warmed up to 70-150 ℃; behind the temperature-stable vinyl monomer and all the other part of auxiliary are added drop-wise in the reactor, reacted 3-8 hour, reduce pressure after waiting the vinyl monomer overwhelming majority to be converted into polymkeric substance; remove unreacted monomer, the discharging sealing is preserved.
In order further to realize purpose of the present invention, preferred temperature 110-130 ℃; 4-5 hour preferred reaction time, monomer conversion is more satisfactory.
The resulting polymer polyester polyol of the present invention can be used as a kind of modified polyalcohol and isocyanate reaction, according to different ingredients, can be used for dissimilar polyurethane products, be preferred for polyurethane shoe at the bottom of, flexible PU foam, but be not limited to this.
Dispersion agent of the present invention, polymer polyester all there is good dispersion effect, resulting polymer polyester polyol product shelf-stable, modest viscosity, this polymer polyester polyol is used for elastomerics fields such as the soft bubble of polyester system, sole and can plays significant modification and fall close effect, improved load, the dimensional stability of low density goods greatly.
The resulting polymer polyester polyol of the present invention can be by adjusting the foamy percentage of open area at the bottom of being used for polyurethane shoe, with the raising loading strength, significantly reduce guarantee under the sole density situation sole have preferably dimensional stability and draw high, tear strength, and then can reduce the sole cost.
(4) embodiment: followingly only the specific embodiment of the present invention is illustrated, but be not limited thereto:
Embodiment 1:
Getting the 300g hydroxyl value is adipic acid ester and the 16.5g MALEIC ANHYDRIDE of 56mgKOH/g (molecular weight 2000); add the stainless steel cauldron that has contact thermometer and nitrogen protection; be warmed up to 160 ℃, under this temperature, kept 1-2 hour, add the 0.016g tetrabutyl titanate then; and be warmed up to 220 ℃; react and cool to 120 ℃ after 3 hours, feed 10g oxyethane, be reacted to acid number and drop to 3.0mgKOH/g stopped reaction when following; decompression obtains dispersion agent 1.
With the 500g hydroxyl value is that 76mgKOH/g (polyester polyol of molecular weight 1500) and 16g dispersion agent 1 join in the glass four-hole bottle of 1000ml, is warmed up to 120 ± 5 ℃ under the nitrogen protection; Get in 70g vinylbenzene, 87.5g vinyl cyanide, 4.3g Diisopropyl azodicarboxylate and 1.5g lauryl mercaptan and the glass jar and mix, this compound average rate is added drop-wise in the glass four-hole bottle, rate of addition is moderate, keeping reacting balance carries out, afterreaction was complete substantially in about 5 hours, obtained polymer polyester polyol 1, and polymer polyester 1 hydroxyl value is 52-60mgKOH/g, viscosity is 5200mPa.s (40 ℃), shelf-stable under the normal temperature.
Embodiment 2:
With the 300g hydroxyl value is that adipate polyester and the 20g fumaric acid of 76mgKOH/g (molecular weight 1500) joins in the glass four-hole bottle, add 20g glycol ether reaction decompression after two hours after 5 hours in 220 ℃ of reactions, acid number is reduced to 3.0mgKOH/g when following, be cooled to 100 ℃, dropping 150g contains the vinylbenzene of Diisopropyl azodicarboxylate, dropwise the reaction 1 hour after the decompression remove free monomer, obtain dispersion agent 2.
With the 500g hydroxyl value is that polyester and the 18g dispersion agent 2 of 76mgKOH/g (molecular weight 1500) joins the glass four-hole bottle, is warmed up to 115 ℃; Get 130g vinylbenzene, 40g vinyl cyanide, 20g methyl acrylate, 2.5g Diisopropyl azodicarboxylate and 1.4g lauryl mercaptan, with mix in the glass jar, mixed liquor at the uniform velocity is added drop-wise in the glass four-hole bottle, begin decompression after 3 hours and remove unreacted monomer, obtain polymer polyester polyol 2, the viscosity of polymer polyester polyol 2 is 6000mPa.s (40 ℃), and hydroxyl value is about 52mgKOH/g, and amount is 25% admittedly contain approximately.
Embodiment 3:
Getting the 600g hydroxyl value is the adipate polyester adding glass four-hole bottle of 112mgKOH/g (molecular weight 1000), other gets 150g vinylbenzene, 30g vinyl cyanide, 3.5g Diisopropyl azodicarboxylate, 30g dispersion agent 2 and mixes, in about 115 ℃, be added drop-wise in the glass four-hole bottle, evenly stir in the dropping process, the control rate of addition prevents the temperature upper punch, be incubated 2.5 hours again after dropwising, free monomer is deviate from decompression, cooling, discharging, obtain polymer polyester polyol 3, this polymer polyester is 5000mPa.s at 40 ℃ of following viscositys, stable storing under the normal temperature.
Application Example 1: the application of polymer polyester polyol in sole
The resulting polymer polyester of the present invention can be used at the bottom of the polyurethane shoe, it can be used as polyol component and uses separately, also can be used with other polyester polyol, and the adding of polymer polyester polyol can be adjusted the foamy percentage of open area, improve loading strength, reduce sole density.
Auxiliary agent when polymer polyester of the present invention is applied to sole has chainextender, whipping agent, catalyzer, pigment etc.Wherein chainextender has ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 1,2-propylene glycol etc., preferred ethylene glycol, 1,4-butyleneglycol; Whipping agent is a water; Catalyzer has triethylene diamine (33% ethylene glycol or Diethylene Glycol solution), two lauric acid diisobutyl tin, stannous octoate, two (dimethyl aminoethyl) ether etc., preferred triethylene diamine and stannous octoate.
What deserves to be explained is that in addition the polymer polyester that this invention obtains is owing to have from the surely effect of bubble, so can save silicone oil.
As shown in table 1, it is even that polyester polyol, catalyzer, chainextender and water are pressed table 1 mixed, and be preheating to 45-50 ℃; To be preheating to 45 ℃ then must join in the polyol blends by the MDI performed polymer in proportion, stirs 3-5 second, pour in the sole test piece grinding tool, and matched moulds, in 60 ℃ of slaking 5-6 branches, depanning obtains testing test piece, and room temperature cure is test performance after 48 hours.
Table 1: sole test piece prescription and salient features
| Prescription | Comparative Examples of the big end | Big-sole formula | Comparative Examples of the middle end | Middle sole formula |
| Polymer polyester | ??0 | ??63 | ??0 | ??45 |
| Conventional polyester (molecular weight 1500) | ??80 | ??17 | ??80 | ??35 |
| Conventional polyester (molecular weight 2000) | ??10 | ??10 | ??10 | ??10 |
| ??EG | ??12 | ??10 | ??7.0 | ??6.0 |
| ??H 2O | ??0.55 | ??0.50 | ??1.0 | ??1.0 |
| Silicone oil | ??0.30 | ??/ | ??0.30 | ??/ |
| ??DC-EG | ??0.5 | ??0.5 | ??0.6 | ??0.6 |
| ??1027 | ??0.5 | ??0.5 | ??0.6 | ??0.6 |
| Index (performed polymer NCO=19%) | ??1.02 | ??1.02 | ??1.0 | ??1.0 |
| Work the time [s] of sending out | ??9 | ??8 | ??8 | ??7 |
| The tack-free time [s] | ??50 | ??40 | ??47 | ??39 |
| Free density [g/cm 3] | ??0.22 | ??0.20 | ??0.15 | ??0.15 |
| Molding density [g/cm 3] | ??0.43 | ??0.39 | ??0.30 | ??0.28 |
| Shrinking percentage [%] | ??＜1％ | ??0.8％ | ??＜1％ | ??0.8％ |
| Tensile strength [MPa] | ??5.7 | ??5.5 | ??2.2 | ??2.3 |
| Productive rate [%] is stretched in fracture | ??350 | ??340 | ??300 | ??290 |
| Hardness (shoreA) | ??60 | ??70 | ??30 | ??35 |
| Tear strength [kN/m] | ??13.9 | ??14.5 | ??4.9 | ??5.3 |
Application Example 2: the application of polymer polyester polyol in flexible PU foam
The resulting polymer polyester of the present invention can cooperate with common soft bubble polyester, be used for the soft bubble of polyester system polyurethane, because the fabulous perforate of polymer polyester polyol, for soft bubble provides good dimensional stability and uniform foam structure, kept the inherent characteristics of polyester simultaneously: high-tear strength.This exploitation for the soft polyester bubble provides more vast potential for future development.
| Soft bubble prescription | Prescription one | Prescription two |
| Polymer polyester | ??25 | ??25 |
| Conventional polyester (molecular weight 1500) | ??25 | ??25 |
| ??DEOA | ??0.25 | ??0.5 |
| Water | ??1.75 | ??1.75 |
| Silicone oil 1 | ??0.05 | |
| Silicone oil 2 | ??0.15 | ??0.2 |
| Catalyzer 1 | ??0.06 | |
| Catalyzer 2 | ??0.35 | ??0.22 |
| ??PM-200 | ??7.0 | |
| ??MDI-50 | ??28 | |
| ??TDI(80/20) | ??24 | |
| ??Index | ??1.0 | ??1.0 |
| Service temperature | Room temperature | Room temperature |
| Work the time [s] of sending out | ??8 | ??15 |
| The hit the ceiling time [s] | ??53 | ??50 |
| Foam density [kg/m 3] | ??40 | ??40 |
| Foam is described | Abscess is fine and closely woven | Random hole foam |
Claims (15)
1, a kind of polymer polyester polyol, it is characterized in that in the presence of dispersion agent and other auxiliary agent, vinyl monomer generates by in-situ polymerization in the base polyester polyvalent alcohol, and this polymer polyester polyol is an external phase with the base polyester, is disperse phase with the polymer beads.
2, a kind of polymer polyester polyol according to claim 1, it is characterized in that described base polyester polyvalent alcohol is a kind of or any several mixture in hexanodioic acid kind polyester polyvalent alcohol, Tetra hydro Phthalic anhydride (terephthalic acid) the kind polyester polyvalent alcohol, the functionality of base polyester polyvalent alcohol is in the 2-5 scope, molecular weight is at 500-3000, and acid number is less than 5mgKOH/g.
3, a kind of polymer polyester polyol according to claim 2, it is characterized in that described hexanodioic acid kind polyester polyvalent alcohol be hexanodioic acid-glycols, hexanodioic acid-Diethylene Glycol class, hexanodioic acid-1.4 butyleneglycol class, hexanodioic acid-ethylene glycol-glycol ether class, hexanodioic acid-ethylene glycol-butyleneglycol class, hexanodioic acid-glycol ether-butyleneglycol class or hexanodioic acid with glycol ether, glycerine, the composite production of the different small molecular alcohols of neopentyl glycol polyester polyol in a kind of or several mixture arbitrarily.
4, a kind of polymer polyester polyol according to claim 2 is characterized in that described Tetra hydro Phthalic anhydride (terephthalic acid) kind polyester polyvalent alcohol is phthalic anhydride-glycol ether class, phthalic anhydride-glycols, phthalic anhydride-glycerols or with phthalic anhydride and glycol ether, several different small molecular alcohols of glycerine a kind of in the composite aromatics polyester polyol that makes or several mixture arbitrarily arbitrarily.
5, a kind of polymer polyester polyol according to claim 1 is characterized in that described vinyl monomer is a kind of in vinylbenzene, vinyl cyanide, divinyl, vinyl toluene, ethyl styrene, vinylformic acid, acrylate, the methyl methacrylate or composite arbitrarily between them.
6, a kind of polymer polyester polyol according to claim 1, it is characterized in that described auxiliary agent is the free radical reaction initiator, comprise isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate, a kind of in the persulphate or composite arbitrarily between them.
7, a kind of polymer polyester polyol according to claim 1, it is characterized in that described auxiliary agent is a chain-transfer agent, comprise a kind of in methyl alcohol, Virahol, butanone, iodoform, iodine, lauryl mercaptan, preferred butanone, the lauryl mercaptan or composite arbitrarily between them.
8, a kind of polymer polyester polyol according to claim 1 is characterized in that described dispersion agent is to make by base polyester and the monomer reaction that contains unsaturated link(age), and its consumption is 2%-10%.
9, a kind of polymer polyester polyol according to claim 8 is characterized in that containing unsaturated acid in the described dispersion agent, is fumaric acid, MALEIC ANHYDRIDE or composite arbitrarily between them.
10, a kind of polymer polyester polyol according to claim 9, it is characterized in that described dispersion agent be with the polyester macromolecule of molecular weight 1000-4000 100-150 ℃ with the fumaric acid reaction that is equivalent to polyester 0.5-2.0 times mole number, after reacting completely, at 100-120 ℃ with ethylene oxide-capped, after end capping is complete, under 0.07-0.09MPa vacuum tightness, reduce pressure, make after removing free oxyethane.
11, a kind of polymer polyester polyol according to claim 9, it is characterized in that described dispersion agent is under the esterifying catalyst effect, react with the fumaric acid of 0.5-2.0 times of polyester macromolecule mole number or MALEIC ANHYDRIDE and 0.5-2.0 times of polyester macromolecule mole number small molecular alcohol down at 200 ℃ with the polyester macromolecule of molecular weight 1000-4000, reduce to 3.0mgKOH/g when acid number and make when following.
12, a kind of polymer polyester polyol according to claim 9, it is characterized in that described dispersion agent is under the esterifying catalyst effect, following at 200 ℃ fumaric acid and the small molecular alcohol with 0.5-2.0 times of polyester macromolecule mole number with the polyester macromolecule of molecular weight 1000-4000 reacts, when acid number is reduced to 3.0mgKOH/g when following, be cooled to 100-130 ℃, add the vinyl monomer that is equivalent to macromonomer mass fraction 30%-70%, be equivalent to macromonomer molfraction 0.5-1.2 initiator doubly, react after 1-4 hour, be decompressed to vacuum tightness 0.07-0.09MPa, remove unreacted monomer and make.
13, according to claim 11 or 12 described a kind of polymer polyester polyols, it is characterized in that described synthetic dispersing agent catalyst for esterification reaction is titanium, tin and antimony class catalyzer, comprise a kind of in two lauric acid diisobutyl tin, tetrabutyl titanate and antimonous oxide, the tetrabutyl titanate or composite arbitrarily between them, the catalyst consumption scope is at 30-300ppm.
14, a kind of polymer polyester polyol according to claim 1 is characterized in that described polymer polyester polyol is the oyster white thick liquid, and acid number is less than 3.0mgKOH/g, and 40 ℃ of viscosity are at 1500-6000mPa.s; The polymer beads stable existence is in the external phase polyester, and the particle size range 50-500nm of polymer beads, molecular weight are at 6000-15000, and the content in polymer polyester polyol is 5%-30%.
15, the production technique of the described a kind of polymer polyester polyol of claim 1; its feature is as follows: base polyester polyvalent alcohol, dispersion agent and part of auxiliary are joined in the reactor; under nitrogen protection, be warmed up to 70-150 ℃; behind the temperature-stable vinyl monomer and all the other part of auxiliary are added drop-wise in the reactor; reacted 3-8 hour; reduce pressure after being converted into polymkeric substance Deng the vinyl monomer overwhelming majority, remove unreacted monomer, the discharging sealing is preserved.
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| US5830944A (en) * | 1994-03-31 | 1998-11-03 | Basf Aktiengesellschaft | Preparation of polymeric polyesterols |
| TWI290933B (en) * | 2000-07-31 | 2007-12-11 | Mitsui Takeda Chemicals Inc | Method and apparatus for producing polyester polyol, polyester polyol and polyurethane foam |
| JP4154654B2 (en) * | 2002-09-13 | 2008-09-24 | アキレス株式会社 | Method for producing rigid polyurethane foam |
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Assignee: Guangdong Wanhua Rongwei Polyurethane Ltd. Assignor: Yantai Wanhua Polyurethane Co., Ltd. Contract fulfillment period: 2008.11.25 to 2014.11.30 contract change Contract record no.: 2009990000139 Denomination of invention: Polymer polyester polyol, its producing process and its use Granted publication date: 20070228 License type: Exclusive license Record date: 2009.3.2 |
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Address after: 264001 No. 7 happy South Road, Zhifu District, Shandong, Yantai Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 264001 No. 7 happy South Road, Zhifu District, Shandong, Yantai Patentee before: Yantai Wanhua Polyurethane Co., Ltd. |