CN101240054B - Imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance and manufacturing method thereof - Google Patents
Imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance and manufacturing method thereof Download PDFInfo
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- CN101240054B CN101240054B CN2007100197306A CN200710019730A CN101240054B CN 101240054 B CN101240054 B CN 101240054B CN 2007100197306 A CN2007100197306 A CN 2007100197306A CN 200710019730 A CN200710019730 A CN 200710019730A CN 101240054 B CN101240054 B CN 101240054B
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- Prior art keywords
- resin
- leather
- hydrolysis resistance
- weather
- batches
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 230000007062 hydrolysis Effects 0.000 title claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000010985 leather Substances 0.000 title claims abstract description 15
- 239000002649 leather substitute Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229920000151 polyglycol Polymers 0.000 claims abstract description 8
- 239000010695 polyglycol Substances 0.000 claims abstract description 8
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 239000004970 Chain extender Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000013256 coordination polymer Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003054 adipate polyester Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
高耐水解、耐候性合成革用仿皮树脂，是以聚酯型聚二醇己内酯为关键材料，与异氰酸酯聚合，然后在催化剂的作用下进行扩链反应而得。该树脂具有高耐水解功能和耐候性功能及机械性能，其耐水解能力达到在户外38℃-40℃长期使用达5-10年的水平，在5％氢氧化溶液中浸泡后耐水解能力达到3年以上，质量稳定可靠。The imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance is obtained by using polyester polyglycol caprolactone as the key material, polymerizing with isocyanate, and then performing chain extension reaction under the action of a catalyst. The resin has high hydrolysis resistance, weather resistance and mechanical properties. Its hydrolysis resistance can reach the level of long-term use outdoors at 38°C-40°C for 5-10 years. After soaking in 5% hydroxide solution, the hydrolysis resistance can reach More than 3 years, stable and reliable quality.
Description
Technical field
The present invention relates to a kind of leather imitation resin for synthetic leather, refer in particular to a kind of imitation leather resin, the method for making this resin is provided simultaneously with high hydrolysis resistance function and high-weatherability leather usefulness.
Background technology
Existing hydrolysis resin on the market, be to adopt PTMEG (PTMG) dibasic alcohol and adipate polyester to make base mateiral, wherein the PTMEG Weather resistant heat resistant is poor, the adipate polyester hydrolytic resistance is poor, still do not have in the market and both had the high hydrolysis resistance function, simultaneously again with the leather imitation resin for synthetic leather of high-weatherability and better mechanical property.
Summary of the invention
Invention is just in order to overcome above-mentioned deficiency, the leather imitation resin for synthetic leather of a kind of high hydrolysis resistance, high-weatherability is provided, main innovate point be in the component polyvalent alcohol with polyester type polyglycol caprolactone (PCL-220CPB) as base resin, itself and isocyanic ester carry out prepolymerization reaction, and the segmented structure of product is more rationalized.Specific implementation process is: high hydrolysis resistance, weatherability leather imitation resin for synthetic leather is characterized in that the weight proportion of each component is:
Molecular weight is 2000 polyglycol caprolactone 60-85%
Isocyanic ester 15-40%
Add:
Adopt polyester type polyglycol caprolactone (PCL-220CPB) as base resin among the present invention, it is the critical material of high hydrolysis resistance function and weathering resistance function.
Ethylene glycol that uses among the present invention (MEG) or 1.4 butyleneglycols (1.4BD) are made chainextender, and dibutyl tin laurate or organo-bismuth are made catalyzer, and organo-bismuth can make product toxicity reduce as catalyzer, safer environmental protection, and N dimethyl formamide DMF makes solvent.
This high hydrolysis resistance, the manufacture method of weatherability leather imitation resin for synthetic leather is: be 2000 polyglycol caprolactone (PCL-220CPB) with molecular weight by the component weight proportion, isocyanic ester transfers pH value between 4.6-5.1 with the phosphoric acid of trace, being warming up to 75 ℃-80 ℃ carried out prepolymerization reaction 1-1.5 hour, being cooled to 50 ℃-55 ℃ again dilutes with part N dimethyl formamide (DMF), drop into catalyzer, drop into chainextender in batches, drop into again batch remaining solvent DMF according to the viscosity growth pattern, until reaction viscosity to 10 ± 20,000 CP.S, drop into methyl alcohol and carry out termination reaction, be warming up to 60 ℃-70 ℃ discharging in insulation reaction 0.5-1 hour packings.
Adopt chain extension method in batches in this manufacture method.Be generally more than three batches, the best in four batches.Except that last, the input weight of each batch chainextender is the 40-50% that last time adds the back surplus, and last chainextender adopts the mode that slowly splashes into.
The input amount of solvent is that viscosity according to material in the operation changes and decide among the present invention, generally speaking, does not need the solubilizing agent dilution after dropping into chainextender for the first time, begins for the second time, adds behind the chainextender because of the viscosity rising at every turn, all needs to dilute with solvent.
Imitation leather resin of the present invention, be to be critical material with polyester type polyglycol caprolactone (PCL-220CPB), with the isocyanic ester polymerization, under the effect of catalyzer, carry out chain extending reaction then and get, this resin has high hydrolysis resistance function and weathering resistance function and mechanical property, its hydrolysis ability reaches out of doors the level that 38 ℃ of-40 ℃ of life-time service reach 5-10, soaks back hydrolysis ability and reach more than 3 years in 5% onium hydroxide solution, and steady quality is reliable.
Specific implementation method
Embodiment 1, at 75 parts of molecular weight 2000 PCL-220CPB, among 25 parts the isocyanic ester MDI, transfer pH value to 4.8 with micro-phosphoric acid, be warming up to 75 ℃ of reactions 1.2 hours, being cooled to 55 ℃ of input DMF dilutes for 60 parts, drop into 0.03 part of catalyzer organo-bismuth, drop into totally 3 parts of chainextender MEG in three batches, first drops into MEG1.5 part, second batch is dropped into MEG0.7 part, drop into DMF50 part, the 3rd batch is dropped into remaining MEG, and the reaction process medium viscosity constantly rises, add 90 parts of solvent DMF again, when viscosimetric reaches 80,000 CP.S, drop into 0.4 part of termination reaction agent methyl alcohol, be warming up to 60 ℃ of insulation reaction discharging in 1 hour packing.
Embodiment 2, with 60 parts of molecular weight 2000 PCL-220CPB, among 40 parts of isocyanic ester MDI, phosphoric acid with trace is transferred pH value to 5.1, be warming up to 80 ℃ of reactions 1 hour, being cooled to 50 ℃ of input DMF50 parts dilutes, drop into 0.02 part of catalyzer dibutyl tin laurate, drop into totally 6 parts of chainextenders in four batches, first drops into 2.8 parts of 1.4 butyleneglycols, second batch is dropped into 1.6 parts of 1.4 butyleneglycols, drops into 100 parts of solvent DMF, and the 3rd batch is dropped into 0.64 part of chainextender 1.4 butyleneglycol, drop into 60 parts of solvent DMF, the 4th batch is dropped into 1.4 remaining butyleneglycols, drops into 65 parts of solvent DMF, and viscosimetric has reached 100,000 CP.S, drop into 0.5 part of termination reaction of termination reaction agent methyl alcohol, be warming up to 65 ℃ of insulation reaction discharging in 0.5 hour packing.
Embodiment 3, with 85 parts of molecular weight 2000 PCL-220CPB, among 15 parts of isocyanic ester MDI, transfer pH value to 4.6 with an amount of phosphoric acid, be warming up to 75 ℃ of reactions 1.5 hours, being cooled to 52 ℃ of input DMF40 parts dilutes, drop into 0.05 part of catalyzer dibutyl tin laurate, drop into 5 parts of chainextenders in four batches, first drops into chainextender MEG2.5 part, second batch is dropped into chainextender MEG1.25 part, drops into 110 parts of solvent DMF, and the 3rd batch is dropped into chainextender MEG0.5 part, drop into 50 parts of solvent DMF, the 4th batch is dropped into remaining MEG, drops into 100 parts of solvent DMF, and viscosimetric has reached 120,000 CP.S, drop into 0.2 part of termination reaction of termination reaction agent methyl alcohol, be warming up to 70 ℃ of insulation reaction discharging in 0.8 hour packing.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100197306A CN101240054B (en) | 2007-02-08 | 2007-02-08 | Imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100197306A CN101240054B (en) | 2007-02-08 | 2007-02-08 | Imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101240054A CN101240054A (en) | 2008-08-13 |
| CN101240054B true CN101240054B (en) | 2011-10-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100197306A Expired - Fee Related CN101240054B (en) | 2007-02-08 | 2007-02-08 | Imitation leather resin for synthetic leather with high hydrolysis resistance and weather resistance and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101240054B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812229B (en) * | 2010-04-02 | 2012-06-20 | 宜兴市新光科技有限公司 | Heat-insulating and shock-absorbing protective film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5180392A (en) | 1975-01-10 | 1976-07-13 | Kuraray Co | SENSHOKU SEIRYOKONAHORIURETANNO SEIZOHO |
| US4098747A (en) * | 1975-06-20 | 1978-07-04 | Interox Chemicals Limited | Polyurethane adhesives having high peel strength at 70° C |
| JPS60206817A (en) | 1984-03-30 | 1985-10-18 | Sanyo Chem Ind Ltd | Production of polyurethane |
| US5312865A (en) * | 1990-06-15 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | Coating compositions |
-
2007
- 2007-02-08 CN CN2007100197306A patent/CN101240054B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5180392A (en) | 1975-01-10 | 1976-07-13 | Kuraray Co | SENSHOKU SEIRYOKONAHORIURETANNO SEIZOHO |
| US4098747A (en) * | 1975-06-20 | 1978-07-04 | Interox Chemicals Limited | Polyurethane adhesives having high peel strength at 70° C |
| JPS60206817A (en) | 1984-03-30 | 1985-10-18 | Sanyo Chem Ind Ltd | Production of polyurethane |
| US5312865A (en) * | 1990-06-15 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | Coating compositions |
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| Publication number | Publication date |
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| CN101240054A (en) | 2008-08-13 |
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Granted publication date: 20111005 Termination date: 20160208 |
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