CN103254425B - End-blocking copolyamide PUR and manufacture method thereof - Google Patents
End-blocking copolyamide PUR and manufacture method thereof Download PDFInfo
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- CN103254425B CN103254425B CN201210036477.6A CN201210036477A CN103254425B CN 103254425 B CN103254425 B CN 103254425B CN 201210036477 A CN201210036477 A CN 201210036477A CN 103254425 B CN103254425 B CN 103254425B
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- acid
- capping reagent
- copolyamide
- reaction
- methyl
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229920000305 Nylon 6,10 Polymers 0.000 claims abstract description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001361 adipic acid Substances 0.000 claims abstract description 7
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 7
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 150000004702 methyl esters Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical group OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 2
- IBMRTYCHDPMBFN-UHFFFAOYSA-N monomethyl glutaric acid Chemical compound COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OSYQOBUUFRGFNG-UHFFFAOYSA-N Sebacic acid monomethyl ester Chemical compound COC(=O)CCCCCCCCC(O)=O OSYQOBUUFRGFNG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000002311 glutaric acids Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a kind of end-blocking copolyamide PUR and manufacture method thereof, manufacture method comprises the steps: to react more than one in more than one in adipic acid or decanedioic acid, hexamethylene diamine, decamethylene diamine or caprolactam and water, row pressure, treat that row pressure terminates, add the end-capping reagent of the 0.5-5% of carboxylic acid gross weight, in-0.05～0.08mpa reaction, obtain end-blocking copolyamide.The present invention uses end-capping reagent, realizes controlling molecular weight to copolyamide, improves molecular weight distribution, owing to end-capping reagent has hydrophobic group, and the shortcoming simultaneously overcoming the copolyamide PUR moisture absorption.
Description
Technical field
The present invention relates to a kind of copolyamide PUR and preparation method thereof.
Technical background
Copolyamide PUR, is that a kind of PUR prepared for lining cloth, its molecular weight and molecular weight distribution are owing to being subject to
The impurity that contains in material proportion, material, reaction condition, the impact in reaction time are difficult to control to level of hope, Ren Men
Produce control time, generally use empirically regular sampling analysis as control device, but reality usually do well or do not accomplish (as
During detection, molecular weight has been above desired value), and molecular weight and distribution thereof are the biggest on the impact of the serviceability of PUR
, owing to the amido of its high relative contents of existence or the carboxyl of little molecule make the resistance to water of PUR substantially be deteriorated, wide point
Cloth makes the overall permeability of PUR be deteriorated, but little molecular moiety is likely to result in excessive permeation and makes lining cloth unholiness, meanwhile, eventually
Only molecular end mainly amido or the carboxyl of reaction also makes its easy moisture absorption.
Summary of the invention
It is an object of the invention to provide a kind of end-blocking copolyamide PUR and manufacture method thereof, to overcome prior art to deposit
Drawbacks described above.
The manufacture method of the end-blocking copolyamide PUR of the present invention, comprises the steps: in adipic acid or decanedioic acid
More than one, more than one and water in hexamethylene diamine, decamethylene diamine or caprolactam, temperature be 180-200 DEG C, pressure be
React 3-6 hour under 0.65～0.85MPa, row pressure, treat that row pressure terminates, add the end-capping reagent of the 0.5-5% of carboxylic acid gross weight,
At a temperature of 220-230 DEG C, it is decompressed to-0.05～0.08mpa reaction 20～60 minutes, obtains end-blocking copolyamide；
Total amido: total carboxyl=1.02-1.03:1；
Described total amido refers to the total moles of amido in above-mentioned material, and total carboxyl refers to carboxyl in above-mentioned material
Total moles.
The preparation method of described end-capping reagent, comprises the steps:
The end-capping reagent of the present invention is cyano carboxylic acid's methyl esters, and the method for preparation comprises the steps:
(1) by dicarboxylic acids in the presence of a catalyst, reacting with methyl alcohol, the reaction time is 0.2-4 hour, reaction
Temperature is 80-120 DEG C, and reaction pressure, at 0.04-0.09Mpa, is then decompressed to-0.095-0.098Mpa, deviates from product
The water that mono methyl dicarboxylate, dibasic acid esters and esterification generate；
Then collect mono methyl dicarboxylate, rectificating method can be used to be collected；
Described dicarboxylic acids is selected from adipic acid, decanedioic acid or glutaric acid；
Described catalyst is selected from phosphoric acid, p-methyl benzenesulfonic acid or resin cation；
Dicarboxylic acids is 2-8:1 with the weight ratio of methyl alcohol；
(2) mix with ammonia after mono methyl dicarboxylate being gasified, carry out amination dehydration, reaction temperature in the presence of a catalyst
Degree is 360-420C, and air speed is 1.5-2.5h-1, from product, then collect described end-capping reagent-cyano carboxylic acid's methyl esters；
Mono methyl dicarboxylate with the weight ratio of ammonia is:
Mono methyl dicarboxylate: ammonia=1: 0.05～0.2；
Described catalyst is alundum (Al2O3) or ZSM-5 molecular sieve；
The present invention uses end-capping reagent, realizes controlling molecular weight to copolyamide, improves molecular weight distribution, due to end-capping reagent
There is hydrophobic group, the shortcoming simultaneously overcoming the copolyamide PUR moisture absorption.
Detailed description of the invention
Embodiment 1
The preparation of end-capping reagent:
Take 202 grams of decanedioic acid, 61.5 grams of methyl alcohol put into thermometer, stirring, reflux condenser four-hole bottle in, then
Add p-methyl benzenesulfonic acid 1 gram, reflux 2 hours at 84 DEG C, sample analysis decanedioic acid, it is completely converted into ester；
In rectifying column, under absolute pressure 2 millimetres of mercury, collect 122-126 DEG C of cut, obtain the decanedioic acid of purity 99.1%
Mono-methyl 148 grams；
In fixed bed reactors, add spherical alundum (Al2O3) 12.5 grams, with weight space velocity 1.57/h-1I.e. 19.7 grams/
Hour flow be continuously added to sebacic acid monomethyl ester toward gasifier ester, simultaneously with weight space velocity 0.15/h-1The stream of i.e. 1.87/ hour
Amount gram is passed through ammonia, and gasifier exit temperature is 450 DEG C.Reaction temperature is 380 DEG C；
Effluent is condensed, dehydration, rectifying, i.e. obtain end-capping reagent-9 cyano group methyl pelargonate.
The preparation of end-blocking copolyamide:
In 1 liter of autoclave, add decanedioic acid 56.5 grams, decamethylene diamine 15.5 grams, adipic acid 29.2 grams, hexamethylene diamine 12.8
Gram, caprolactam 65 grams and 45 grams of water.
Being warming up to 180 DEG C, pressure is increased to 0.85MPa, row pressure after keeping 1 hour.
The row pressure time is to keep 200 DEG C to normal pressure, temperature in 0.6 hour.Add above-mentioned end-capping reagent 4.1 under nitrogen protection
Gram, it is decompressed to-0.075MPa at 220 DEG C, reacts 1.2 hours, obtain the copolyamide 159.2 grams of end-blocking.
Using melt index determination method (160 DEG C, 2.16kg) to detect, melt index is 29.5；
Employing gel permeation chromatography mensuration molecular weight distribution, molecular weight distribution=weight-average molecular weight/number-average molecular weight, for
3.64；
Under conditions of environment temperature 24-35C, relative humidity 56-88%, baking oven weight reduction is used to carry out moisture absorption detection,
Result is 1.02%.
Embodiment 2
The preparation of end-capping reagent:
Take 132 grams of glutaric acids, 56.3 grams of methyl alcohol, put in four-hole bottle, be subsequently adding phosphoric acid 0.65 gram, anti-80 DEG C of backflows
Answering 0.5 hour, sample analysis, glutaric acid is completely converted into methyl esters；
Under absolute pressure 3 millimetres of mercury, 69-72 DEG C of cut is collected in rectifying, obtains monomethyl glutarate 96.4 grams；
In fixed bed reactors, add bar shaped ZSM-5 molecular sieve 18 grams, with weight space velocity 2.0/H-1I.e. 36 Grams Per Hours
Flow be passed through monomethyl glutarate toward gasifier continuously, weight space velocity 0.27/H simultaneously-1Flow that is 4.86 Grams Per Hour be passed through
Liquefied ammonia.Gasifier exit temperature is 480 DEG C, and reaction temperature controls at 450 DEG C.Effluent is condensed, be dehydrated, rectifying obtains cyano group fourth
Acid methyl esters.
The preparation of end-blocking copolyamide:
In 1 liter of autoclave, add 85.2 grams of decanedioic acid, 29.2 g of adipic acid 58 restrain oneself diamines, 67.8 restrain oneself lactams and
38.4 gram water.Through being warming up to 200 DEG C, pressure is increased to 0.65MPa, keeps 1.5 hours, row pressure.Then, above-mentioned preparation is added
End-capping reagent 7.2 grams, is warming up to 240 DEG C, is decompressed to-0.06MPa, reacts and within 2 hours, must block copolyamide 218.5 grams.
Using melt index determination method to detect, melt index is 30.3；
Employing gel permeation chromatography mensuration molecular weight distribution, molecular weight distribution=weight-average molecular weight/number-average molecular weight, for
3.58；
Under conditions of environment temperature 24-35C, relative humidity 56-88%, baking oven weight reduction is used to carry out moisture absorption detection,
Result is 0.97%.
Claims (1)
1. block copolyamide PUR manufacture method, it is characterised in that by more than one in adipic acid or decanedioic acid, oneself
More than one and water in diamines, decamethylene diamine or caprolactam, temperature be 180～200 DEG C, pressure be 0.65～0.85MPa
Lower reaction 3～6 hours, the mol ratio of total amido and total carboxyl is 1.02～1.03:1；Row pressure, treats that row pressure terminates, and adds carboxylic acid
The 0.5 of gross weight～the end-capping reagent of 5%, described end-capping reagent is cyano carboxylic acid's methyl esters, at a temperature of 220～230 DEG C, be decompressed to-
0.05～0.08 MPa reacts 20～60 minutes, obtains end-blocking copolyamide, and the preparation method of described end-capping reagent, including as follows
Step:
(1) by dicarboxylic acids in the presence of a catalyst, reacting with methyl alcohol, the reaction time is 0.2～4 hour, reaction temperature
Degree is 80～120 DEG C, and reaction pressure, at 0.04～0.09 MPa, is then decompressed to-0.095～0.098MPa, and abjection reaction is produced
The water that thing mono methyl dicarboxylate, dibasic acid esters and esterification generate；Then mono methyl dicarboxylate is collected；
(2) mixing with ammonia after mono methyl dicarboxylate being gasified, carry out amination dehydration in the presence of a catalyst, reaction temperature is
360～420 DEG C, air speed is 1.5～2.5h-1, from product, then collect described end-capping reagent-cyano carboxylic acid's methyl esters；
Dicarboxylic acids in described step (1) is selected from adipic acid, decanedioic acid or glutaric acid；Dicarboxylic acids with the weight ratio of methyl alcohol is
2～8:1；Described catalyst is selected from phosphoric acid, p-methyl benzenesulfonic acid or resin cation；
In step (2), mono methyl dicarboxylate is 1: 0.05～0.2 with the weight ratio of ammonia；Described catalyst is alundum (Al2O3)
Or ZSM-5 molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210036477.6A CN103254425B (en) | 2012-02-17 | 2012-02-17 | End-blocking copolyamide PUR and manufacture method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210036477.6A CN103254425B (en) | 2012-02-17 | 2012-02-17 | End-blocking copolyamide PUR and manufacture method thereof |
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| Publication Number | Publication Date |
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| CN103254425A CN103254425A (en) | 2013-08-21 |
| CN103254425B true CN103254425B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210036477.6A Active CN103254425B (en) | 2012-02-17 | 2012-02-17 | End-blocking copolyamide PUR and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114163632A (en) * | 2022-01-04 | 2022-03-11 | 上海东睿化学有限公司 | Anti-yellowing copolyamide and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850887A (en) * | 1972-09-13 | 1974-11-26 | Usm Corp | Lactam copolyamides for adhesive use |
| US4024116A (en) * | 1974-09-21 | 1977-05-17 | Basf Aktiengesellschaft | Hot-melt adhesive based on copolyamides from caprolactam and alkylene dicarboxylic acid salts of polyether diamine |
| CN1884419A (en) * | 2006-07-03 | 2006-12-27 | 无锡殷达尼龙有限公司 | Use of decamethylene diamine in preparing copolyamide hot sol |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7001979B2 (en) * | 2002-06-14 | 2006-02-21 | H.B. Fuller Licensing & Financing Inc. | Polyamide and composition and article including same |
-
2012
- 2012-02-17 CN CN201210036477.6A patent/CN103254425B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850887A (en) * | 1972-09-13 | 1974-11-26 | Usm Corp | Lactam copolyamides for adhesive use |
| US4024116A (en) * | 1974-09-21 | 1977-05-17 | Basf Aktiengesellschaft | Hot-melt adhesive based on copolyamides from caprolactam and alkylene dicarboxylic acid salts of polyether diamine |
| CN1884419A (en) * | 2006-07-03 | 2006-12-27 | 无锡殷达尼龙有限公司 | Use of decamethylene diamine in preparing copolyamide hot sol |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
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| CN103254425A (en) | 2013-08-21 |
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Denomination of invention: Terminated copolyamide hot melt adhesive and its manufacturing method Effective date of registration: 20220721 Granted publication date: 20160817 Pledgee: Industrial Bank Co.,Ltd. Shanghai Branch Pledgor: SHANGHAI DONGRUI CHEMICAL Co.,Ltd. Registration number: Y2022310000135 |
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Denomination of invention: Capped copolyamide hot melt adhesive and its manufacturing method Effective date of registration: 20230726 Granted publication date: 20160817 Pledgee: Industrial Bank Co.,Ltd. Shanghai Jinshan Branch Pledgor: SHANGHAI DONGRUI CHEMICAL Co.,Ltd. Registration number: Y2023310000400 |
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Address after: 639 Xiasheng Road, Jinshan District, Shanghai, May 12, 2015 Patentee after: Shanghai Dongrui New Materials Co.,Ltd. Country or region after: China Address before: Room 1104, Building 1, No. 1089 Laoweiqing Road, Jinshanwei Town, Jinshan District, Shanghai, December 2010 Patentee before: SHANGHAI DONGRUI CHEMICAL Co.,Ltd. Country or region before: China |