CN102167797A - Hydrolysis-resistant dimer acid type polyurethane and preparation method thereof - Google Patents
Hydrolysis-resistant dimer acid type polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses hydrolysis-resistant dimmer acid type polyurethane which comprises 100 parts of polyester polylol, 18-35 parts of diisocyanate, 2-5 parts of chain extender, 0-5 parts of castor oil and 180-360 parts of organic solvent; and the preparation method comprises the following steps: performing decompression dehydration on the polyester polylol at the temperature of 110-120 DEG C for 2-3 hours, then reducing the temperature to 60-80 DEG C, adding the organic solvent and the diisocyanate, reacting for 1-3 hours at the temperature of 60-80 DEG C, obtaining a prepolymer, then adding the chain extender, the castor oil and the organic solvent, reacting for 1-3 hours at the temperature of 60-80 DEG C, adding the diisocyanate and the organic solvent into the obtained polymer, reacting for 2-5 hours at the temperature of 60-80 DEG C, and obtaining the solvent type polyurethane containing a dimmer acid structure unit. Considering from two aspects, namely economy and benefit, the hydrolysis-resistant dimmer acid type polyurethane with low cost is synthesized, and the hydrolysis-resistant dimmer acid type polyurethane has obvious application and market prospects.
Description
Technical field
The invention belongs to the polyurethane field in the macromolecular material, particularly dimer acid type urethane of a kind of hydrolytic resistance and preparation method thereof.
Background technology
Urethane has good low-temperature resistance, anti tear and performance such as wear-resisting, is widely used in fields such as leather, coating, sizing agent and seal gum.According to the difference of soft segment structure, urethane can be divided into polyether-type and PAUR.In contrast to polyether(poly)urethane, PAUR has better mechanical property and dyeability.Yet, contain a large amount of polar groups in the polyurethane molecular backbone structure, make polyurethane material absorb moisture easily.The PAUR that contains ester group for soft segment structure, after moisture penetration was delivered in the molecular backbone chain structure, the as easy as rolling off a log hydrolysis that causes ester group caused the reduction of polyurethane molecular amount, reduce the mechanical strength of material, even may make the polyurethane material inefficacy have an accident.On the other hand, after the polyurethane material suction, plastification takes place.After the plasticising, the interior and intermolecular hydrogen bond action of polyurethane molecular descends, and causes the polyurethane material mechanical properties decrease, and material shape also may be out of shape.This is a reversing process.The bad large-scale application of PAUR in industry that hindered of hydrolytic resistance difference and water tolerance also makes urethane in use may become the potentially dangerous body.
Present stage, the raw material of urethane is from the petrochemical industry resource.Yet, along with the petrochemical industry resource day by day totally, the development of urethane is certain to be affected.Utilize natural reproducible resource all to replace or partly replace the petrochemical material of urethane, can solve and be subject to this bottleneck of petrochemical industry resource.Adopt dimeracid all to replace or part replaces the raw material polyester diol of small molecules diprotic acid synthesis of polyurethane, both can reduce the use of petrochemical industry resource, Sustainable development also can improve hydrolytic resistance, water tolerance and the thermostability of urethane.Using dimer acid polyester dibasic alcohol method for producing polyurethanes to be disclosed in for example Chinese patent CN101503611A and CN101613451A.Yet in the prior art, the usage quantity of dimeracid is no more than 30% of mixed dibasic acid weight, does not reduce the use of petrochemical industry resource significantly, and the degree that hydrolytic resistance improves is also little.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of dimer acid type urethane of hydrolytic resistance with not enough.This urethane not only has good hydrolytic resistance, water tolerance and thermostability, and adopts whole replacements of natural reproducible resource dimeracid or part to replace the small molecules diprotic acid, reduces the use of petrochemical industry resource.
Another object of the present invention provides the preparation method of above-mentioned urethane.
Purpose of the present invention is achieved through the following technical solutions: a kind of dimer acid type urethane of hydrolytic resistance is made up of the following component of meter by weight:
Described polyester polyol prepares by the following method: polyprotonic acid and small molecules dibasic alcohol are pressed the mol ratio COOH/OH=1 of functional group: mix at 1.1～1: 1.7, stirs under nitrogen atmosphere and heat up 120 ℃～175 ℃, behind reaction 3～5h, be warming up to 190 ℃～210 ℃, react 3～5h again, sampling detecting acid number treats that acid number is less than 20mgKOH/g, stop logical nitrogen, vacuumize, under vacuum, react sampling detecting acid number, when treating that acid number is less than or equal to 1mgKOH/g, stopped reaction.
Described polyprotonic acid is a dimeracid, or the weight that the mixing acid of dimeracid and small molecules diprotic acid and dimeracid account for mixing acid is not less than 30%.The preferred dimeracid of described polyprotonic acid.
The dimeracid full name is a dimer (fatty acid) yl, by two C
18Unsaturated fatty acids (as oleic acid, linolic acid etc.) in the presence of catalyzer, the dicarboxylic acid that generates through polyreaction.The commodity dimeracid is with C
36Dimer is main mixture, wherein, contains a small amount of C
54Tripolymer, the isomerized C of part
18Monomer.In the process of preparation dimeracid, because raw materials used C
18Contain the oleic acid of two keys and the linolic acid of two two keys in the unsaturated fatty acids, the dimeracid of in fact producing will contain non-ring structure and ring texture.Its ratio is decided on oleic acid in the raw material and linoleic content.The then non-ring structure of oleic acid content height is many, and linoleic acid content height then ring texture is many, and the commodity dimeracid is actually the mixture of multiple complex construction.Because dimeracid contains the hydrophobic aliphatic hydrocarbon structure of long-chain, and contains the part ring texture, introduce in the polyurethane system, can improve the hydrolytic resistance and the mechanical strength of urethane.
Described small molecules diprotic acid is preferably more than one mixing in hexanodioic acid, m-phthalic acid and the terephthalic acid
Described small molecules dibasic alcohol is preferably neopentyl glycol, 1,4-butyleneglycol, 1, more than one mixing in 6-hexylene glycol, ethylene glycol, glycol ether and the dipropylene glycol; Described small molecules dibasic alcohol is more preferably one or both mixing in neopentyl glycol and the glycol ether.
Described vulcabond is more than one mixing in aromatic diisocyanate, aliphatic diisocyanate and the alicyclic diisocyanate; Described vulcabond is preferably diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), polyphenyl polymethylene polyisocyanates (PAPI), 1,6-hexamethylene diisocyanate (HDI), 1,3,3-trimethylammonium-5-isocyanato-1-isocyanato methylcyclohexane (isophorone diisocyanate, IPDI) and dicyclohexyl methyl hydride-4, more than one mixing in 4 '-vulcabond (HMDI).
Described chainextender is 1,4-butyleneglycol, ethylene glycol, neopentyl glycol, 1, more than one mixing of 6-hexylene glycol, glycol ether, dipropylene glycol, quadrol, diethylenetriamine and triethylene tetramine.
Described Viscotrol C is the glyceryl ester of lipid acid, has the long-chain fat base.And the hydroxyl average functionality is about 2.7, can increase the degree of crosslinking of urethane.Viscotrol C is introduced in the polyurethane molecular structure, can further improve hydrolytic resistance, water tolerance and the thermostability of polyurethane material.
Described organic solvent is N, dinethylformamide, dioxan (1, the 4-dioxane), vinyl acetic monomer, N-BUTYL ACETATE, methylethylketone, more than one mixing of toluene and dimethylbenzene.
The preparation method of the dimer acid type urethane of above-mentioned hydrolytic resistance comprises following operation steps:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2～3h, are cooled to 60～80 ℃, add 60～120 parts of organic solvents and 12～23 parts of vulcabond,, obtain performed polymer at 60～80 ℃ of reaction 1～3h;
(2) chain extending reaction: add 2～5 parts of chainextenders in step (1) gained performed polymer, 0～5 part of Viscotrol C and 60～120 parts of organic solvents are at 60～80 ℃ of reaction 1～3h;
(3) polyreaction: add 6～12 parts of vulcabond and 60～120 parts of organic solvents to step (2) resulting polymers,, obtain containing the solvent borne polyurethane of dimeracid structural unit at 60～80 ℃ of reaction 2～5h.
The dimer acid type urethane of above-mentioned hydrolytic resistance is applied to prepare leather, coating, sizing agent or seal gum.
The present invention has following advantage and effect with respect to prior art:
(1) adopts the vacuum fusion method, will contain the polyprotonic acid of dimeracid weight 30%～100% and the raw material polyester diol that the polycondensation of small molecules dibasic alcohol obtains urethane; All replace or part replaces petrochemical industry resource small molecules diprotic acid with the natural reproducible resource dimeracid, not only can reduce the use of petrochemical industry resource, Sustainable development, and can break away from the constraint of petrochemical industry resource.Contain the hydrophobic aliphatic hydrocarbon and the alicyclic hydrocarbon structure of long-chain with this polyester glycol synthetic urethane, can improve the hydrolytic resistance and the thermostability of urethane.
(2) the natural reproducible resource dimeracid is easy to get, and is with low cost, thereby reduced the synthetic cost of dimer acid type urethane.
(3) adopt and to contain long-chain fat hydrocarbon and polyhydric Viscotrol C chainextender, can further improve the hydrolytic resistance and the water tolerance of urethane as urethane.
(4) the present invention considers from economy and benefit two aspects, has synthesized the dimer acid type urethane of the low hydrolytic resistance of cost, has tangible application and market outlook.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation polyprotonic acid is a dimeracid, the mol ratio COOH/OH=1 of functional group: 1.10 polyester polyol: with 583 parts of dimeracid (high-purity dimeric acids, acid number 193mgKOH/g, Guangrao Welfare Resin Factory) and 105 parts of neopentyl glycol join in the reactor, under nitrogen atmosphere, stir and heat up.At 120 ℃ of reaction 2h, 140 ℃ of reaction 1h, 175 ℃ of reaction 2h.Be warming up to 210 ℃ then and react 4h again, sampling detecting acid number, acid number equals 13mgKOH/g, stops logical nitrogen, vacuumizes.React 2h under vacuum, sampling detecting acid number, acid number are 0.48mgKOH/g, and discharging is a light brown liquid, and hydroxyl value is 42.32mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 70 ℃, add 100 parts of N, dinethylformamide and 20 parts of diphenylmethanediisocyanates at 70 ℃ of reaction 2h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 5 part 1,4-butyleneglycol and 100 parts of N, dinethylformamide is at 70 ℃ of reaction 3h;
(3) polyreaction: add 9 parts of diphenylmethanediisocyanates and 100 parts of N to step (2) resulting polymers, dinethylformamide at 70 ℃ of reaction 4h, obtains dimer acid type urethane.
Present embodiment gained dimer acid type urethane is translucent, good stability.
Embodiment 2
The preparation polyprotonic acid is a dimeracid, the mol ratio COOH/OH=1 of functional group: 1.55 polyester polyol: with 583 parts of dimeracid (high-purity dimeric acids, acid number 193mgKOH/g, Guangrao Welfare Resin Factory, down with), 100 parts of neopentyl glycol and 80 part 1, the 6-hexylene glycol joins in the reactor, stirs under nitrogen atmosphere and heats up.At 120 ℃ of reaction 2h, 140 ℃ of reaction 1h, 175 ℃ of reaction 2h.Be warming up to 210 ℃ then and react 4h again, sampling detecting acid number, acid number equals 12mgKOH/g, stops logical nitrogen, vacuumizes.React 2h under vacuum, sampling detecting acid number, acid number are 0.57mgKOH/g, and discharging is a light brown liquid, and hydroxyl value is 54.82mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110 ℃ of decompression dehydration 2h, are cooled to 60 ℃, add 70 parts of N, dinethylformamide, 50 parts of toluene and 13 parts of tolylene diisocyanates at 60 ℃ of reaction 3h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 4 parts of neopentyl glycol, 5 parts of Viscotrol C, 70 parts of N, dinethylformamide and 50 parts of toluene are at 80 ℃ of reaction 1h;
(3) polyreaction: add 7 parts of tolylene diisocyanates to step (2) resulting polymers, 70 parts of N, dinethylformamide and 50 parts of toluene at 60 ℃ of reaction 5h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type urethane is translucent, good stability.
Embodiment 3
The preparation polyprotonic acid is that dimeracid accounts for mixing polyprotonic acid weight 89%, the mol ratio COOH/OH=1 of functional group: 1.48 polyester polyol: 408 parts of dimeracids, 52 parts of hexanodioic acids, 120 parts of neopentyl glycol and 20 parts of ethylene glycol are joined in the reactor, react by embodiment 1 described method, obtaining acid number is 0.62mgKOH/g, discharging is a light brown liquid, hydroxyl value is 49.43mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 120 ℃ of decompression dehydration 2h, are cooled to 80 ℃, add 35 parts of N, dinethylformamide, 35 parts of dioxan and 12 part 1, the 6-hexamethylene diisocyanate at 80 ℃ of reaction 1h, obtains performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 2 parts of ethylene glycol, 1 part of diethylenetriamine, 35 parts of N, dinethylformamide and 35 parts of dioxan are at 60 ℃ of reaction 3h;
(3) polyreaction: add 6 parts of tolylene diisocyanates to step (2) resulting polymers, 35 parts of N, dinethylformamide and 35 parts of dioxan at 80 ℃ of reaction 2h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
Embodiment 4
The preparation polyprotonic acid is that dimeracid accounts for mixing polyprotonic acid weight 90%, the mol ratio COOH/OH=1 of functional group: 1.48 polyester polyol: with 408 parts of dimeracids, 47 parts of terephthalic acids, 100 parts of neopentyl glycol and 50 part 1, the 4-butyleneglycol joins in the reactor, react by embodiment 1 described method, obtaining acid number is 0.55mgKOH/g, discharging is a light brown liquid, and hydroxyl value is 51.34mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 65 ℃, add 50 parts of N, dinethylformamide, 40 parts of N-BUTYL ACETATEs and 23 parts of isophorone diisocyanates at 65 ℃ of reaction 3h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 4 parts of glycol ethers, 4 parts of Viscotrol C, 50 parts of N, dinethylformamide and 40 parts of N-BUTYL ACETATEs are at 70 ℃ of reaction 3h;
(3) polyreaction: add 12 parts of isophorone diisocyanates to step (2) resulting polymers, 50 parts of N, dinethylformamide and 40 parts of N-BUTYL ACETATEs at 65 ℃ of reaction 4h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
Embodiment 5
The preparation polyprotonic acid is that dimeracid accounts for mixing polyprotonic acid weight 80%, the mol ratio COOH/OH=1 of functional group: 1.39 polyester polyol: 390 parts of dimeracids, 95 parts of hexanodioic acids, 100 parts of neopentyl glycol and 90 parts of glycol ethers are joined in the reactor, react by embodiment 1 described method, obtaining acid number is 0.87mgKOH/g, discharging is a light brown liquid, hydroxyl value is 48.89mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 60 ℃, add 40 parts of N, dinethylformamide, 20 parts of vinyl acetic monomers and 12 part 1, the 6-hexamethylene diisocyanate at 60 ℃ of reaction 3h, obtains performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 2 parts of quadrols, 40 parts of N, dinethylformamide and 20 parts of vinyl acetic monomers are at 65 ℃ of reaction 2h;
(3) polyreaction: add 6 parts of diphenylmethanediisocyanates to step (2) resulting polymers, 40 parts of N, dinethylformamide and 20 parts of vinyl acetic monomers at 60 ℃ of reaction 4h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
Embodiment 6
The preparation polyprotonic acid is that dimeracid accounts for mixing polyprotonic acid weight 80%, the mol ratio COOH/OH=1 of functional group: 1.70 polyester polyol: 390 parts of dimeracids, 95 parts of m-phthalic acids, 115 parts of neopentyl glycol and 140 parts of dipropylene glycol are joined in the reactor, react by embodiment 1 described method, obtaining acid number is 0.59mgKOH/g, discharging is a light brown liquid, hydroxyl value is 61.64mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 60 ℃, add 50 parts of N, dinethylformamide, 53 parts of methylethylketones and 21 parts of dicyclohexyl methane diisocyanates at 60～80 ℃ of reaction 3h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 3 part 1, the 6-hexylene glycol, 1 part of triethylene tetramine, 3 parts of Viscotrol C, 50 parts of N, dinethylformamide and 53 parts of methylethylketones are at 70 ℃ of reaction 3h;
(3) polyreaction: add 10 parts of dicyclohexyl methane diisocyanates to step (2) resulting polymers, 50 parts of N, dinethylformamide and 53 parts of methylethylketones at 60 ℃ of reaction 5h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
Embodiment 7
The preparation polyprotonic acid is that dimeracid accounts for mixing polyprotonic acid weight 80%, the mol ratio COOH/OH=1 of functional group: 1.45 polyester polyol: 85 parts of dimeracids, 198 parts of hexanodioic acids and 219 parts of neopentyl glycol are joined in the reactor, react by embodiment 1 described method, obtaining acid number is 0.65mgKOH/g, discharging is a light brown liquid, hydroxyl value is 54.75mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 60 ℃, add 70 parts of N, dinethylformamide, 40 parts of dimethylbenzene and 18 parts of diphenylmethanediisocyanates at 60 ℃ of reaction 3h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 5 parts of dipropylene glycol, 70 parts of N, dinethylformamide and 40 parts of dimethylbenzene are at 65 ℃ of reaction 2h;
(3) polyreaction: add 9 parts of diphenylmethanediisocyanates to step (2) resulting polymers, 70 parts of N, dinethylformamide and 40 parts of dimethylbenzene at 60 ℃ of reaction 5h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
Comparative Examples
The preparation polyester polyol: 292 parts of hexanodioic acids and 255 parts of neopentyl glycol are joined in the reactor, react by embodiment 1 described method, obtaining acid number is 0.44mgKOH/g, and discharging is a colourless liquid, and hydroxyl value is 65.27mgKOH/g, obtains polyester polyol.
Preparation dimer acid type urethane:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2h, are cooled to 70 ℃, add 70 parts of N, dinethylformamide, 30 parts of dimethylbenzene and 17 parts of polyphenyl polymethylene polyisocyanates at 70 ℃ of reaction 2h, obtain performed polymer;
(2) chain extending reaction: in step (1) gained performed polymer, add 3 part 1, the 4-butyleneglycol, 3 parts of Viscotrol C, 70 parts of N, dinethylformamide and 30 parts of dimethylbenzene are at 80 ℃ of reaction 1h;
(3) polyreaction: add 8 parts of polyphenyl polymethylene polyisocyanates to step (2) resulting polymers, 70 parts of N, dinethylformamide and 30 parts of dimethylbenzene at 80 ℃ of reaction 3h, obtain dimer acid type urethane.
Present embodiment gained dimer acid type polyurethane transparent, good stability.
The urethane that dimer acid type urethane that embodiment 1-7 is prepared and Comparative Examples obtain carries out water-intake rate test, hydrolytic resistance test, and method is as follows:
The water-intake rate testing method: the film forming matter that drying is good, m weighs
0, immerse in 30 ℃ of deionized waters of constant temperature.After soaking certain hour, the surface of taking out and drying film forming matter with filter paper rapidly, m weighs
1Formula is:
The hydrolytic resistance testing method: the film forming matter that drying is good, m weighs
0, immersing in 37 ℃ of about 0.1mol/LNaOH of constant temperature (pH=13) solution, behind the immersion certain hour, after taking-up and the drying, m weighs
2Formula is:
Test result is as shown in table 1:
The hydrolytic resistance of table 1 embodiment 1-7 gained dimer acid type urethane
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. the dimer acid type urethane of a hydrolytic resistance is characterized in that the dimer acid type urethane of described hydrolytic resistance is made up of the following component of meter by weight:
Described polyester polyol prepares by the following method: polyprotonic acid and small molecules dibasic alcohol are pressed the mol ratio COOH/OH=1 of functional group: mix at 1.1～1: 1.7, stirs under nitrogen atmosphere and be warming up to 120 ℃～175 ℃, behind reaction 3～5h, be warming up to 190 ℃～210 ℃, react 3～5h again, sampling detecting acid number treats that acid number is less than 20mgKOH/g, stop logical nitrogen, vacuumize, under vacuum, react sampling detecting acid number, when treating that acid number is less than or equal to 1mgKOH/g, stopped reaction;
Described polyprotonic acid is that the mixing acid of dimeracid or dimeracid and small molecules diprotic acid and weight that dimeracid accounts for mixing acid are not less than 30%;
Described organic solvent is N, dinethylformamide, dioxan, vinyl acetic monomer, N-BUTYL ACETATE, methylethylketone, more than one mixing of toluene and dimethylbenzene.
2. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 1, it is characterized in that: described small molecules diprotic acid is more than one mixing in hexanodioic acid, m-phthalic acid and the terephthalic acid.
3. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 1, it is characterized in that: described small molecules dibasic alcohol is a neopentyl glycol, 1,4-butyleneglycol, 1, more than one mixing in 6-hexylene glycol, ethylene glycol, glycol ether and the dipropylene glycol.
4. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 3, it is characterized in that: described small molecules dibasic alcohol is one or both mixing in neopentyl glycol and the glycol ether.
5. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 1, it is characterized in that: described vulcabond is more than one mixing in aromatic diisocyanate, aliphatic diisocyanate and the alicyclic diisocyanate.
6. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 5, it is characterized in that: described vulcabond is diphenylmethanediisocyanate, tolylene diisocyanate, polyphenyl polymethylene polyisocyanates, 1,6-hexamethylene diisocyanate, 1,3,3-trimethylammonium-5-isocyanato-1-isocyanato methylcyclohexane and dicyclohexyl methyl hydride-4, more than one mixing in 4 '-vulcabond.
7. according to the dimer acid type urethane of the described a kind of hydrolytic resistance of claim 1, it is characterized in that: described chainextender is 1,4-butyleneglycol, ethylene glycol, neopentyl glycol, 1, more than one mixing of 6-hexylene glycol, glycol ether, dipropylene glycol, quadrol, diethylenetriamine and triethylene tetramine.
8. the preparation method of the dimer acid type urethane of the described hydrolytic resistance of each claim of claim 1-7 is characterized in that comprising following operation steps:
(1) prepolymerization reaction: 100 parts of polyester polyols behind 110～120 ℃ of decompression dehydration 2～3h, are cooled to 60～80 ℃, add 60～120 parts of organic solvents and 12～23 parts of vulcabond,, obtain performed polymer at 60～80 ℃ of reaction 1～3h;
(2) chain extending reaction: add 2～5 parts of chainextenders in step (1) gained performed polymer, 0～5 part of Viscotrol C and 60～120 parts of organic solvents are at 60～80 ℃ of reaction 1～3h;
(3) polyreaction: add 6～12 parts of vulcabond and 60～120 parts of organic solvents to step (2) resulting polymers,, obtain containing the solvent borne polyurethane of dimeracid structural unit at 60～80 ℃ of reaction 2～5h.
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| WO2020124543A1 (en) * | 2018-12-21 | 2020-06-25 | Dow Global Technologies Llc | Two-component solvent-based adhesive composition |
| CN113330089A (en) * | 2018-12-21 | 2021-08-31 | 陶氏环球技术有限责任公司 | Two-component solvent-based adhesive composition |
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| CN112708100A (en) * | 2020-12-29 | 2021-04-27 | 福建汇得新材料有限公司 | Polyurethane resin and preparation method and application thereof |
| CN114316196A (en) * | 2021-12-29 | 2022-04-12 | 上海华峰新材料研发科技有限公司 | Hydrolysis-resistant polyurethane damping material and preparation method and application thereof |
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