CN1060097A - Hexanolactam and poly-dihydric alcohol process for copolymerization - Google Patents
Hexanolactam and poly-dihydric alcohol process for copolymerization Download PDFInfo
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- CN1060097A CN1060097A CN 90105552 CN90105552A CN1060097A CN 1060097 A CN1060097 A CN 1060097A CN 90105552 CN90105552 CN 90105552 CN 90105552 A CN90105552 A CN 90105552A CN 1060097 A CN1060097 A CN 1060097A
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- dihydric alcohol
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Abstract
The present invention relates to the process for copolymerization of hexanolactam and poly-dihydric alcohol, it is characterized in that taking not add carboxylic acid or organic amine, and with hexanolactam and poly-dihydric alcohol direct copolymerization in the presence of water, the preparation polyether amide copolymer, then through casting, pelletizing, extraction drying, fusion reel off raw silk from cocoons, drawing-off, obtain other physical index and the close fibers of pure PA-6 fiber such as soft, intensity.
Description
The present invention relates to the method that caprolactam and poly-dihydric alcohol copolymerization prepare polyether-amide co-polymer (PEEA).
Pilot plant writes according to Beijing synthon, introduces in " polyamide fibre production " that petrochemical industry press published in 1976, and the molecular weight stabilizer of caprolactam hydrolytic polymerization mainly is carboxylic acid and organic amine; EP156,035 earlier with the polyamide segment of caprolactam hydrolysis Cheng Handuan carboxyl in the presence of carboxylic acid (as adipic acid etc.), and then makes polyether ester amides with poly-dihydric alcohol (as polyoxyethylene glycol) esterification.This method esterification is difficulty, and esterification yield is not high, and technology is complicated.US3654370 will hold carboxyl to convert the end amido to poly-dihydric alcohol (as polyoxyethylene glycol) amination in the presence of high temperature, high pressure, noble metal catalyst, and then prepare polyether-amide with the end carboxyl reaction of polymeric amide.Perhaps,, will hold carboxyl to convert the end carboxyl to the reaction of poly-dihydric alcohol and di-carboxylic acid, and then with the end amido reaction of polymeric amide, prepare polyether ester amides.Introduce in the first phase in 1989 " Beijing Institute of Clothing Tech's journal " P1～12 page, add poly-dihydric alcohol (as PEG in the caprolactam hydrolytic polymerization system, addition is less than 10% of the caprolactam feeding quantity), find that poly-dihydric alcohol plays inhibition, the polymeric amide of making does not have practical value.
The objective of the invention is to solve in traditional caprolactam hydrolysis polymerization process and can not directly add the difficult problem that poly-dihydric alcohol carries out copolymerization, the copolyamide that contains polyether segment of excellent properties such as that preparation has is hydrophilic, antistatic, antifouling, shock resistance.
The present invention is achieved in that and takes not add carboxylic acid or organic amine, but caprolactam and poly-dihydric alcohol are directly carried out copolymerization in the presence of water, and preparation contains the copolyamide of polyether segment.Concrete processing step is: at first with 100 parts of caprolactams (weight), 1.5～40 parts of (weight) poly-dihydric alcohols, 0.5～5 parts of (weight) water add reactors and molten be mixed even, then under nitrogen protection in normal pressure or pressurization (≤1.5MPa), reacted 1.5～8 hours under 210～290 ℃ of conditions; (overbottom pressure≤3.4 * 10 under reduced pressure again
4Pa), 220～290 ℃, reacted 0.5～6.0 hour; Or under 220～290 ℃ of conditions of normal pressure, reacted 2～10 hours.Reaction finishes back casting under nitrogen protection, pelletizing then, extracts, is drying to obtain polyether-amide multipolymer (PEEA).
The present invention takes not add carboxylic acid or organic amine, and the direct copolymerization in the presence of water with caprolactam and poly-dihydric alcohol makes the polyether-amide multipolymer, is characterized in: (1), need not add carboxylic acid or organic amine; (2), poly-dihydric alcohol without hindrance poly-effect in above-mentioned copolymerization system; Played the effect of molecular weight stabilizer and reacting movable agent, significantly fast reaction speed; (3), the ehter bond in the poly-dihydric alcohol molecule is very steady in the ordinary course of things, but is easy to decompose when having acid, water to exist simultaneously under hot conditions, do not add organic acid and then can avoid; (4), do not add organic acid and organic amine molecular weight stabilizer, make poly-dihydric alcohol can directly participate in ring-opening reaction, the terminal hydroxy group activity of poly-dihydric alcohol is strengthened greatly, helps the formation of ester bond.Otherwise reaction is difficult to obtain high-molecular weight product with practical value; (5), compared with prior art, can realize that single stage method is directly with in the polyethers key section introducing polymeric amide molecular chain.And avoided in the method for fractional steps, end group concentration is low in the high viscosity reaction system, and speed of response is slow, transformation efficiency is low, waits shortcomings such as mole proportioning difficulty.
Embodiment 1:
Caprolactam 7000g, distilled water 105mI, molecular-weight average are 20,000 poly-dihydric alcohol 1400g, and nitrogen pressure is to 0.25MPa, molten be mixed even after, stir, be heated to 230 ± 10 ℃, reacted 2 hours; Be heated to 250 ± 10 ℃, reacted 2 hours, be decompressed to normal pressure then and be decompressed to overbottom pressure≤3.5 * 10 after 10 minutes again
4Pa, 250 ± 10 ℃ were reacted 4 hours.After reaction finished, casting under the nitrogen protection, extracted, is drying to obtain the section of polyether-amide co-polymer at pelletizing then.220 ℃ of gained copolymerization fusing points, extractable matter (monomer) content is 5.0% before the extraction, co-polymer limiting viscosity (η)=0.60 Grams Per Minute, liter (100mI40% sulfuric acid dissolution polymkeric substance 0.5g).
Co-polymer through strengthening extraction (co-polymer: distilled water=1: 150,90 ℃ 3 hours) after through outer analysis result: 1720cm
-1Hydroxyl in the appearance ester bond (
) absorption peak, 1250cm
-1, 1108cm
-1, 950cm
-1, 850cm
-1The place has occurred
CH
2CH
2O
The absorption peak of group illustrates that polyether segment links to each other with the PA-6 segment with ester bond.
Co-polymer rheological data table (270 ℃ of temperature)
Shearing rate shear-stress viscosity (handkerchief, second)
(second
-1* 10
2) (Pa * 10
3) PEEA PA-6
1.2 17.3 142 65
9.2 56.9 60 61
27.9 164 22 59
245～280 ℃ of fusions of the co-polymer of manufacturing of the present invention section are reeled off raw silk from cocoons, the fiber that obtains of drawing-off then, at 20 ℃, record under the RH65% condition: moisture regain is 7.6% for the 80%(cotton, and pure Pa-6 is 4.3%), the ratio resistance of no oil drying silk is 2.38 * 10
9Ω cm, (20 ℃, RH65%) nothing in week oil silk is than resistance 2.0 * 10 for balance Moisture absorption
8Ω cm.Fiber is soft, and other physical indexs such as intensity are close with pure Pa-6.
Embodiment 2:
Caprolactam 1500g, distilled water 25mI, polypropylene glycol (molecular-weight average 2000) 50g, polytetramethylene glycol (molecular-weight average 1000) 100g, nitrogen pressure to 0.1MPa molten be mixed even after, be heated with stirring to 220 ± 10 ℃ of reactions 1 hour, 240 ± 10 ℃ were reacted 2 hours, 260 ± 10 ℃ were reacted 2.5 hours, and pressure release was reacted 6 hours to 260 ± 10 ℃ of normal pressures then.After the end, nitrogen protection casting, pelletizing, extraction, drying get the polyether-amide multipolymer section that limiting viscosity (η)=0.47 Grams Per Minute rises.
Claims (1)
1, a kind of hexanolactam and poly-dihydric alcohol copolymerization prepare the method for polyether-amide multipolymer, it is characterized in that: hexanolactam and poly-dihydric alcohol direct copolymerization in the presence of water prepares the polyether-amide multipolymer, the weight ratio prescription of described preparation polyether-amide multipolymer is: 100 parts of hexanolactams, 1.5～40 parts of poly-dihydric alcohols, 0.5～5.0 part in water; The reaction pressure temperature-time of described preparation polyether-amide multipolymer: at first be normal pressure or pressurization≤1.5MPa, temperature of reaction is 210～290 ℃, and the reaction times is 1.5～8 hours, and reaction pressure is decompression, overbottom pressure power≤3.4 * 10 then
4Pa, temperature of reaction is 220～290 ℃, the reaction times is 0.5～6 hour, or reacts 2～10 hours down for 220～290 ℃ at normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105552 CN1060097A (en) | 1990-09-18 | 1990-09-18 | Hexanolactam and poly-dihydric alcohol process for copolymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105552 CN1060097A (en) | 1990-09-18 | 1990-09-18 | Hexanolactam and poly-dihydric alcohol process for copolymerization |
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| Publication Number | Publication Date |
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| CN1060097A true CN1060097A (en) | 1992-04-08 |
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ID=4879366
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| Application Number | Title | Priority Date | Filing Date |
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| CN 90105552 Pending CN1060097A (en) | 1990-09-18 | 1990-09-18 | Hexanolactam and poly-dihydric alcohol process for copolymerization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774318A (en) * | 2018-07-12 | 2018-11-09 | 中仑塑业（福建）有限公司 | A kind of antistatic nylon 6 and preparation method thereof |
-
1990
- 1990-09-18 CN CN 90105552 patent/CN1060097A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774318A (en) * | 2018-07-12 | 2018-11-09 | 中仑塑业（福建）有限公司 | A kind of antistatic nylon 6 and preparation method thereof |
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