CN104140520B - High Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and preparation method thereof - Google Patents
High Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and preparation method thereof Download PDFInfo
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- CN104140520B CN104140520B CN201410383713.0A CN201410383713A CN104140520B CN 104140520 B CN104140520 B CN 104140520B CN 201410383713 A CN201410383713 A CN 201410383713A CN 104140520 B CN104140520 B CN 104140520B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses high Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and preparation method thereof, be prepared from by following raw materials in parts by weight: isocyanates, polyol compound, chain extender, antioxidant, reaction terminating agent methyl alcohol, catalyst, addition is the 0.001-0.05% of polyol compound quality; The number-average molecular weight of described polyol compound is 1000-3000; Described polyol compound by PEPA, PPG and polyene polyalcohol in mass ratio for 1:0.8-1.2:0.1-0.3 forms; The total mol ratio of hydroxyl in described isocyanates in isocyano and polyol compound and chain extender is 0.9-1:1; The mol ratio of described polyol compound and chain extender is 1:1.3-1.7. Polyurethane resin of the present invention has been improved more greatly soft resin and can not take into account the problem of high resiliency and high-peeling strength, and product is durable in use, have the market competitiveness.
Description
Technical field
The present invention relates to a kind of polyurethane resin, be specifically related to the high wet type of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and gatherAmmonia ester resin and preparation method thereof.
Background technology
Due to corium resource-constrained, price is high, cannot meet the growing market demand. And Synthetic Leather productRaw material sources are extensive, low price, and good processability, has has met or exceeded the characteristic of natural leather, meets people's completelyLife seek. And Synthetic Leather products material wide material sources, low price, good processability, can meet people's lifeLive and pursue. The application of polyurethane resin aspect synthetic leather is mainly reflected in multiple necks such as clothes, case and bag, footwear, furniture, automobileTerritory, leather is more and more faster with the development speed of polyurethane resin in recent years, in the face of the increasing gradually of the market demand, it is also proposed moreHigh requirement,
At present, men and women's leather shoes, sport footwear market is progressively to the future development of snugness of fit, quality softness, good springiness, resistance toThe product excellent by performance is subject to consumer's welcome most. But existing polyurethane resin is difficult to take into account that modulus is low, good springiness, intensityHigh these three features.
Summary of the invention
The present invention aims to provide high Wet-type polyurethane resin and the preparation side thereof of peeling off of a kind of ultra-soft matter high resiliency hydrolysisMethod, elasticity, intensity and the anti-hydrolytic performance of raising mild polyurethane resin.
Technical solution problem of the present invention adopts following technical scheme:
The high Wet-type polyurethane resin of peeling off of ultra-soft matter high resiliency hydrolysis, prepared by following raw materials in parts by weight andBecome:
Isocyanates
Polyol compound
Chain extender
Antioxidant
Reaction terminating agent methyl alcohol
Organic tin or organo-bismuth class catalyst, addition is the 0.001-0.05% of polyol compound quality;
The number-average molecular weight of described polyol compound is 1000-3000;
Described polyol compound is 1:0.8-by PEPA, PPG and polyene polyalcohol in mass ratio1.2:0.1-0.3 composition;
The molecular weight of described PEPA is 2000, and it is by adipic acid 4000kg, ethylene glycol or BDO2500kg, catalyst Ti isopropyl propionate 0.4kg is prepared from;
The total mol ratio of hydroxyl in described isocyanates in isocyano and polyol compound and chain extender is 0.9-1:1；
The mol ratio of described polyol compound and chain extender is 1:1.3-1.7.
Further, described isocyanates is 4,4 '-methyl diphenylene diisocyanate.
Described PEPA is that degree of functionality is that 2 adipic acid is PEPA;
Described PPG is that degree of functionality is 2 PolyTHF polyalcohol or polyoxypropylene polyol;
Described polyene polyalcohol is that degree of functionality is 2 polybutadiene polyol.
Described chain extender is ethylene glycol, BDO, 1, one or both in 6-hexylene glycol, and wherein two kinds of mixing makeWith being to mix for 0.1:1 ~ 10:1 in molar ratio.
Described antioxidant is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1-1010), 2,2'-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol) (antioxidant 2246).
Another goal of the invention of the present invention is to provide a kind of above-mentioned high wet type of peeling off of ultra-soft matter high resiliency hydrolysisThe preparation method of polyurethane resin, step is as follows:
1) first 60% and the antioxidant that account for polyol compound gross mass are added in organic solvent, formation solid content is 20-30% solution; After stirring, add the 20%-25% that accounts for isocyanates gross mass in 45-50 DEG C of reaction 1-2 hour; Then willRemaining polyol compound adds continuation reaction after 1-2 hour, then adds the 15%-20% that accounts for isocyanates gross mass, makes manyThe mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond in unit's alcoholic compound; Finally admittedly contained in 55-65 DEG C of reactionAmount is that 45-55%, viscosity are the prepolymer of 30-80Pas/75 DEG C;
2) in prepolymer, add chain extender, surplus isocyanates and organic tin or organo-bismuth class catalyst, stir allAfter even, in 75-85 DEG C of continuation reaction 2-5h, in the process of reaction, along with constantly supplementing organic solvent, the increase of system viscosity makesObtain final viscosity and be controlled at 80-120Pas/25 DEG C, after having reacted, add reaction terminating agent methyl alcohol to obtain polyurethane resin.
Further, the moisture content of described polyol compound, isocyanates, chain extender is all less than 500ppm.
The preferred N of described organic solvent, N '-dimethyl formamide (DMF).
The Wet-type polyurethane resin making by above-mentioned formula is applied to synthetic leather and produces, and the leather goods of making have elasticityThe feature good, peel strength is high, anti-hydrolytic performance is good.
Polyurethane resin of the present invention has been improved more greatly elasticity, peel strength and the hydrolysis aspect of soft resinPhysical property, product is durable in use, and product specification is high, has the market competitiveness.
Beneficial effect:
1, prepolymerization reaction temperature of the present invention is low, thereby has ensured molecule segment homogeneity;
2, in first step prepolymerization reaction of the present invention, adopt and in batches MDI is added, make pre-polymerization have comparatively obvious two sectionsThe crystallization of different performance.
, in amount 3, the present invention, polyol compound by PEPA, PPG and polyene polyalcohol in mass ratioFor 1:0.8-1.2:0.1-0.3 composition; And PEPA is by adipic acid 4000kg, ethylene glycol or BDO2500kg, catalyst Ti isopropyl propionate 0.4kg is prepared from, and makes the naval stores of preparation comprehensively excellent at the aspect such as cost, performanceGesture, has that peel strength is high, anti-hydrolytic performance good, and the feature such as good hand feeling.
Detailed description of the invention
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction withDetailed description of the invention, further sets forth the present invention.
In embodiment, each component is as follows respectively below:
EG is ethylene glycol;
BG is BDO;
Described polyol compound is 1:0.8-by PEPA, PPG and polyene polyalcohol in mass ratio1.2:0.1-0.3 composition; Wherein SP-1 is that molecular weight is that 2000 adipic acid is PEPA;
It is 1000,2000 Polyoxypropylene diol that PPG-1, PPG-2 are respectively molecular weight;
It is 1000,2000 PolyTHF dihydroxylic alcohols that PTMG-1, PTMG-2 are respectively molecular weight;
It is 1000,2000 polybutadiene dihydroxylic alcohols that HTPB-1, HTPB-2 are respectively molecular weight;
Antioxidant I-1010 is commercially available antioxidant, entirely four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] seasons penta by nameTetrol ester;
MDI is 4,4 '-methyl diphenylene diisocyanate;
Organo-bismuth is catalysts, and to be wherein better than organotin be to know altogether in industry to the feature of environmental protection of organo-bismuth;
DMF is solvent N, N '-dimethyl formamide, and methyl alcohol is reaction terminating agent.
Embodiment 1:
Raw material and proportioning:
1) first the HTPB-2 of the PTMG-2 of the SP-1 of 750kg, 370kg, 50kg and 3kg antioxidant I-1010 are addedIn organic solvent DMF, the solution that formation solid content is 30%; After stirring, add 130-140kg isocyanates in 45-50 DEG CReaction 1-2 hour; Then the PTMG-1 of remaining 400kg is added and continue reaction after 2 hours, then add 100-120kg differentCyanate, makes in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond; Finally in 65 DEG C of reactionsObtain solid content and be 55%, viscosity is the prepolymer of 80Pas/75 DEG C;
2) in prepolymer, add 100kg chain extender EG, isocyanates 360-390kg and organo-bismuth class catalyst(BiCAT 8106, the leading chemical company of the U.S. is produced) 0.2kg, after stirring, in 75-85 DEG C of continuation reaction 2-5h,In the process of reaction, along with constantly supplementing organic solvent, the increase of system viscosity make final viscosity be controlled at 120Pas/25DEG C, after having reacted, add reaction terminating agent methyl alcohol 2kg to obtain polyurethane resin.
Embodiment 2:
1, raw material and proportioning:
1) first the PPG-1 of the PPG-2 of the SP-1 of 600kg, 400kg, 200kg and 3kg antioxidant I-1010 are addedIn organic solvent DMF, the solution that formation solid content is 20%; After stirring, add 130-150kg isocyanates in 45 DEG C of reactions1 hour; Then the HTPB-1 of remaining 30kg is added and continue reaction after 1 hour, then add 50-60kg isocyanates, makeThe mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond in polyol compound; Finally admittedly contained in 55 DEG C of reactionsAmount is 45%, viscosity is the prepolymer of 30Pas/75 DEG C;
2) in prepolymer, add 100kg chain extender EG, isocyanates 360-390kg and organo-bismuth class catalyst(BiCAT 8106, the leading chemical company of the U.S. is produced) 0.2kg, after stirring, in 75 DEG C of continuation reaction 2h, in reactionProcess in make final viscosity be controlled at 80Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, reactionAfter completing, add reaction terminating agent methyl alcohol 0.5kg to obtain polyurethane resin.
Comparative example 1:
PTMG-2, polyester diol are dissolved in DMF, then add part MDI, make hydroxyl and two in polyol compoundIn isocyanates, the mol ratio 1:1.5 of isocyano carries out prepolymerization reaction, obtains prepolymer. Then in prepolymer, add surplusMDI, catalyst, chain extender EG continue reaction, make polyurethane resin.
In order to verify the performance of the high Wet-type polyurethane resin of peeling off of ultra-soft matter high resiliency hydrolysis of the present invention, willPolyurethane resin prepared by embodiment 1-2 and comparative example 1 is made synthetic leather by existing wet processing, and concrete process hides formula is as follows:
Polyurethane resin 300kg
DMF100kg
H2O2kg
Bleeding agent 4kg
Foam stabilizer 2kg
Wood powder 15kg
Mill base is appropriate
Then draw a design according to synthetic leather industry conventional method, carry out peel strength, hydrolysis test, method of testing refers to closesFinished leather technology, Qu Jianbo etc. write, Chemical Industry Press (2010.3), P127-158 finished leather processing technology, P368 peels offStrength test method, P369 hydrolysis detection method, adopt quick alkaline-resisting survey to peel off, and wet production is please engaged in feel test for a long timeEngineer judge, the results are shown in following table 1.
Table 1
| Physical property | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Resin state | Transparency liquid | Transparency liquid | Light yellow transparent liquid |
| Peel strength N/3cm | 135 | 140 | 100 |
| Hydrolytic resistance N/3cm | 120 | 120 | 75 |
| Feel | Plentiful flexible | Plentiful flexible | Poor compared with plumpness |
As can be seen from Table 1, polyurethane resin of the present invention is all greatly super aspect peel strength, hydrolytic resistance and feelCross ordinary resin.
After testing, the Wet-type polyurethane synthetic leather made from the formula of above-mentioned enforcement, has good resilience, peels off by forceSpend high, durability is superior.
In claims of this description and the application, so-called system, refers to whole reaction system, is exactly all substancesTotal amount. That in above-mentioned embodiment and description, describes just illustrates principle of the present invention, do not depart from the present invention's spirit andUnder the prerequisite of scope, the present invention also has various changes and modifications, and these changes and improvements all fall into claimed model of the present inventionIn enclosing. The claimed scope of the present invention is defined by appending claims and jljl thereof.
Claims (6)
1. the high Wet-type polyurethane resin of peeling off of ultra-soft matter high resiliency hydrolysis, is characterized in that: pressed heavy by following raw materialAmount part is prepared from:
Isocyanates
Polyol compound
Chain extender
Antioxidant
Reaction terminating agent methyl alcohol
Organic tin or organo-bismuth class catalyst, addition is the 0.001-0.05% of polyol compound quality;
The number-average molecular weight of described polyol compound is 1000-3000;
Described polyol compound is 1:0.8-1.2 by PEPA, PPG and polyene polyalcohol in mass ratio:0.1-0.3 composition;
The molecular weight of described PEPA is 2000, and it is by adipic acid 4000kg, ethylene glycol or BDO 2500kg,Catalyst Ti isopropyl propionate 0.4kg is prepared from;
Described PPG is that degree of functionality is 2 PolyTHF polyalcohol or polyoxypropylene polyol;
Described polyene polyalcohol is that degree of functionality is 2 polybutadiene polyol;
The total mol ratio of hydroxyl in described isocyanates in isocyano and polyol compound and chain extender is 0.9-1:1;
The mol ratio of described polyol compound and chain extender is 1:1.3-1.7.
2. polyurethane resin according to claim 1, is characterized in that: described isocyanates is 4,4 '-diphenyl methaneVulcabond.
3. polyurethane resin according to claim 1, is characterized in that: described PEPA is that degree of functionality is oneself of 2Oxalic acid series PEPA.
4. polyurethane resin according to claim 1, is characterized in that: described chain extender be ethylene glycol, BDO,One or both in 1,6-hexylene glycol, wherein two kinds of mixing uses are to mix for 0.1:1 ~ 10:1 in molar ratio.
5. the preparation side of the high Wet-type polyurethane resin of peeling off of ultra-soft matter high resiliency hydrolysis as claimed in claim 1Method, is characterized in that: step is as follows:
1) first 60% and the antioxidant that account for polyol compound gross mass are added in organic solvent, formation solid content is 20-30%Solution; After stirring, add the 20%-25% that accounts for isocyanates gross mass in 45-50 DEG C of reaction 1-2 hour; Then by remainderPolyol compound add and continue reaction after 1-2 hour, then add the 15%-20% that accounts for isocyanates gross mass, make polyalcoholThe mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond in compound; Finally obtaining solid content in 55-65 DEG C of reaction is45-55%, viscosity are the prepolymer of 30-80Pas/75 DEG C;
2) in prepolymer, add chain extender, surplus isocyanates and organic tin or organo-bismuth class catalyst, after stirring,In 75-85 DEG C of continuation reaction 2-5h, in the process of reaction, along with constantly supplementing organic solvent, the increase of system viscosity makesWhole viscosity is controlled at 80-120Pas/25 DEG C, adds reaction terminating agent methyl alcohol to obtain polyurethane resin after having reacted.
6. preparation method according to claim 5, is characterized in that: described polyol compound, isocyanates, chain extenderMoisture content be all less than 500ppm; Described organic solvent is N, N '-dimethyl formamide.
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| CN201410383713.0A CN104140520B (en) | 2014-08-06 | 2014-08-06 | High Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and preparation method thereof |
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| CN201410383713.0A CN104140520B (en) | 2014-08-06 | 2014-08-06 | High Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter high resiliency hydrolysis and preparation method thereof |
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| CN104448221A (en) * | 2014-11-24 | 2015-03-25 | 晋江市闽高纺织科技有限公司 | Polyurethane high-resilience leather clothes and preparation method thereof |
| CN105153398B (en) * | 2015-09-21 | 2018-02-23 | 合肥安利聚氨酯新材料有限公司 | A kind of soft hydrolysis low-crystallinity polyether-type sofa artificial leather wet polyurethane resin and preparation method thereof |
| CN105254834A (en) * | 2015-09-25 | 2016-01-20 | 嘉兴禾欣化学工业有限公司 | Preparation method of high resilience polyurethane resin for synthetic leather |
| CN105153399B (en) * | 2015-09-29 | 2018-04-10 | 合肥安利聚氨酯新材料有限公司 | A kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof |
| CN105199078A (en) * | 2015-10-08 | 2015-12-30 | 合肥安利聚氨酯新材料有限公司 | Medium-soft luggage leather embossing resin for elastic fabrics and preparation method thereof |
| CN105385147A (en) * | 2015-11-20 | 2016-03-09 | 嘉兴洛克化学工业有限公司 | High-resilience polyurethane resin and preparation method thereof |
| CN109970942A (en) * | 2019-01-24 | 2019-07-05 | 扬州工业职业技术学院 | A kind of polyurethane wet bass of cold-resistant hydrolysis and preparation method thereof |
| CN111087566B (en) * | 2019-09-29 | 2021-10-29 | 扬州工业职业技术学院 | Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin |
| CN110684173B (en) * | 2019-10-14 | 2022-01-14 | 浙江华峰合成树脂有限公司 | Super-soft hydrolysis-resistant wet polyurethane resin and preparation method thereof |
| CN111647132B (en) * | 2020-06-09 | 2022-01-07 | 上海华峰超纤科技股份有限公司 | Preparation method and application of low-elasticity polyurethane resin |
| CN114316771B (en) * | 2021-12-29 | 2023-06-02 | 雅涂科技(张家港)有限公司 | Polyurethane coating and preparation method and application thereof |
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