CN1035022C - Ternary copolymer fibre with polyester, polyether and polyorganosiloxane - Google Patents
Ternary copolymer fibre with polyester, polyether and polyorganosiloxane Download PDFInfo
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- CN1035022C CN1035022C CN 92108718 CN92108718A CN1035022C CN 1035022 C CN1035022 C CN 1035022C CN 92108718 CN92108718 CN 92108718 CN 92108718 A CN92108718 A CN 92108718A CN 1035022 C CN1035022 C CN 1035022C
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Abstract
The present invention relates to a ternary random copolymer fiber of polyester, polyether and polysiloxane, which has a high staining degree when the fiber is treated by boiling dye by dispersed dye under normal pressure. The fiber comprises the following components: the addition amount of polyether is from 3% to 10% of the weight of an esterification product; the addition amount of polysiloxane is from 2% to 5% of the esterification product; the addition amount of sterically hindered phenol antioxidant in a composite heat stabilizer is from 0.018% to 0.036% of the weight of the esterification product; the addition amount of phosphonic acid, phosphorous acid or ester thereof is from 0.008% to 0.04% of the weight of the esterification product; the addition amount of a bivalent metal cobalt compound is from 0.006% to 0.038% of the weight of the esterification product. The components become a ternary copolymer through polycondensation at the temperature of 270 to 288 DEG C and at the vacuum degree of 0.35 mmHg. Then a ternary random copolymer fiber is made by conventional melt spinning.
Description
The present invention relates to the fiber that polyester, polyethers, polysiloxanes terpolymer make, particularly the fiber of polyester, polyethers, polysiloxanes ternary statistic copolymer.
Adopt polyethers in the prior art, ester is made the high elasticity flexible fibre, for example JP63-264965 adopts the block copolymer of polyester and polyethers to prepare the multiply fiber, and the disclosed highly elastic fiber of being formed with polyetherester block copolymer and phthalic acid second diester of JP63-227813, manufacture method and prescription thereof as for the JP61-28912l elastomer that then to disclose with 11 methylene diamine and ten dimethylene diamines and poly-alkoxyl ethylene glycol and poly-alkoxyl ethylenediamine be Main Ingredients and Appearance, the fiber that these methods make is to have improved elasticity and heat endurance mostly, but all exist the stock-dye difficulty, the shortcoming that fabric feeling difference and copolymerization rate are slow.
The purpose of this invention is to provide a kind of ternary statistic copolymer fiber and manufacture method thereof with polyester, polyethers and polysiloxanes, the dye uptake height of gained fiber, good heat stability, the good hand touch of fabric, and also its rate of polymerization is also fast when combined polymerization.
Well-known polyester (as polyethylene terephthalate) fiber has mechanical strength and modulus is higher, the advantage that ABRASION RESISTANCE and heat resistance are better, chemical resistance of concrete is strong, but the dyeing difficulty of its fiber.Polyethers is as the property-modifying additive of polyester, the ternary copolymer fibre of gained just can be dyeed with DISPERSE DYES under normal pressure, and the dye-uptake height, the COLOR FASTNESS height, hygroscopicity and antistatic behaviour wait premium properties well, but also exist poor heat stability, as when being processed into fiber, run into its color and luster of higher temperature and physical and mechanical properties variation, particularly its fabric is after 180-200 ℃ of following HEAT SETTING, the fabric feeling variation appears, defect such as its colour changed into yellow.
The main cause of this polyether ester fibre poor heat stability is because exist a large amount of ehter bonds in macromolecular chain, and the oxygen resistence of ehter bond is poor, under higher temperature, meet oxygen and can produce violent thermal oxidative degradation and thermal degradation, so generally be to adopt the method that adds heat stabilizer to suppress its thermal oxidative degradation and thermal degradation, but shortcoming of also having brought the polyether ester fusing point to descend.
The purpose of this invention is to provide a kind of change conventional practice, promptly adopt in polyethers, polyester and to add polysiloxanes and make the ternary statistic copolymer, the heat endurance that reduces the method for ether component amount simultaneously and a kind of because polysiloxanes is provided is more than the polyethers height, so the heat endurance of terpolymer that makes gained is than original polyether ester binary copolymerization object height, the dye-uptake height of fiber, the fiber that fabric feeling is good.
Another object of the present invention provides the method that a kind of ternary polymerization time is shortened greatly, its reason is because alcoholysis reaction aggravation in the course of reaction during traditional polyether ester binary copolymerization, copolycondensation speed descends, so polymerization time increases, and behind the adding polysiloxanes, because the end group reactivity is big, so combined polymerization speed is accelerated.
Now component of the present invention is described in down:
(1) contains the esterification products of a small amount of oligomer
Adopting the direct esterification method is that mol ratio with terephthalic acid (TPA) and ethylene glycol is 1: 1.1-1.3, esterification temperature is from 190 ℃-230 ℃, esterification pressure is the 1.5-2.5 kg/cm, about about 3 hours of esterification time, polycondensation catalyst is antimonous oxide (counting 0.025% with terephthalic acid (TPA) weight), and the esterification products of acetic acid (counting 0.008-0.024% with terephthalic acid (TPA) weight) gained is ethylene glycol terephthalate and the mixture (being designated hereinafter simply as esterification products) that contains a small amount of oligomer.(2) polyethers
Its general formula is HO (C
nH
2nO)
mH
N is 2 multiple in the formula, and m is the integer of 6-100, mean molecule quantity
Be 600-6000, the most frequently used is polyethylene glycol.
Its input amount is that its general formula of 3-10% (3) polysiloxanes of above-mentioned esterification products weight is
R in the formula
1, R
2, R
3And R
4Be Methylethyl or phenyl, m is
The integer of 3-10.Mean molecule quantity is 200-1500
(4) composite thermal stabilizer
A. the antioxidant that has sterically hindered phenol, addition are above-mentioned esterification products weight
0.018-0.036％
B. phosphoric acid, phosphorous acid or its ester class, addition are that above-mentioned carboxylate output is heavy
The 0.008-0.04% of amount
C. divalent metal cobalt compound, its general formula is C
0X
2, X is a halogen in the formula
Plain acetate, addition is the 0.006-of above-mentioned esterification products
0.038％。The condensation temperature of terpolymer is 270-
288 ℃, vacuum is 0.35mmHg.The polycondensation time approximately
About 90 minutes.
With prepared terpolymer section, be spun into fiber with fusion method, test its heat endurance and dye-uptake then, and measure and calculate the initial temperature t of molten preceding oxidation peak with differential thermal analysis (DTA) or difference formula scanning thermometric analysis (DSO)
0, thermal oxide coefficient of stability H (H=SO
2/ SN
2, SO
2Be the area of melting peak under the oxygen condition, SN
2Be the area of melting peak under condition of nitrogen gas), as t
0Value is high, and H value approaches 1, and then the heat endurance of sample is just high, also measures its viscosity of not having the oil silk and falls Δ (η) (Δ (η) is to cut the inherent viscosity that inherent viscosity before the electric seasoning deducts does not have oil thread) Δ (η) is more for a short time and show that the heat endurance of sample is high more.
The following examples elaborate to the present invention, but do not limit the scope of the invention.
Example 1. is with 1660 gram terephthalic acid (TPA)s and 744 grams
Ethylene glycol is put into general esterifying kettle, add antimonous oxide 0.415 gram and acetic acid 0.4 gram, the whole temperature of esterification is 220 ℃, esterification 3 hours, esterification products 1856 gram, drop into mean molecule quantity then and be 4000 polyethylene glycol 72 grams and mean molecule quantity and be 400 polysiloxanes 72 and restrain, cobalt oxide 0.23 gram, phosphoric acid is 0.31 gram, position phenol resistance anti-oxidant Irganox, 1222 (Research Inst. of Chemical Industry, Beijing) 0.42 gram.In temperature is 280 ℃, and vacuum is to carry out polycondensation under the 0.35mmHg 90 minutes, makes terpolymer of the present invention, and its inherent viscosity (η) is 0.702, and fusing point is 252 ℃
The t of this example 1 gained
0Be 201 ℃, H is 0.976, and Δ (η) is 0.063.
The gained terpolymer is cut into slices, fiber is copied in fusion, 3.24 times of 75 ℃ of following drawing-offs, under 180 ℃, heat-treated 15 minutes, record fibrous fracture intensity and reduce to 8.4%, adopt dispersive red dye Samaran Red 2BSL (150) (production of Hochst factory) 10%, bath raio is 1: 100, dyeed 2 hours down at 100 ℃, recording dye-uptake is 89.2%
Comparative example 1 removes and not to add polysiloxanes, and the polycondensation time of copolyesters be outside 121 minutes, all the other conditions are identical with example 1, the polymer that makes its (η) is 0.68, fusing point is 249 ℃, t
0Be 133 ℃, H is 0.547, and Δ (η) is 0.158, and it is 85.9% that fracture strength is reduced to 31.2% dye-uptake.
Example 2, the amount that remove to add mean molecule quantity and be 4000 polyethylene glycol changes 12 grams into, and the ternary polycondensation time is outside 104 minutes, and all the other conditions are identical with example 1, and the various performances of gained terpolymer and spinning see Table 1.
Example 3, the mean molecule quantity that removes polysiloxanes changes 1500 into, and the ternary polycondensation time is outside 98 minutes, and all the other conditions are identical with 1, and the various performances of gained terpolymer and spinning see Table 1.
Example 4, the mean molecule quantity that removes polyethylene glycol changes 1000 into, and the polycondensation time is outside 107 minutes, and all the other conditions are identical with example 1, and the various performances of gained terpolymer and spinning see Table 1.
Example 5. replaces the ethylene glycol except that the polytetramethylene glycol that with molecular weight is 4000, and other condition is identical with example 1, records data and also lists in table 1.Table 1
| 〔η〕 | Fusing point (℃) | t 0 (℃) | H | Δ〔η〕 | (%) falls in fracture strength | Dye-uptake % | |
| Example 1 | 0.702 | 252 | 210 | 0.976 | 0.063 | 8.4 | 89.2 |
| Example 2 | 0.693 | 252 | 192 | 0.955 | 0.097 | 15.8 | 92.1 |
| Example 3 | 0.703 | 254 | 194 | 0.936 | 0.100 | 17.9 | 88.9 |
| Example 4 | 0.687 | 251 | 202 | 0.979 | 0.059 | 8.0 | 93.8 |
| Example 5 | 0.683 | 250 | 108 | 0.933 | 0.103 | 16.8 | 87.7 |
| Comparative example 1 | 0.68 | 249 | 133 | 0.547 | 0.158 | 31.2 | 85.9 |
Described in last table and example, the advantage of the ternary statistic copolymer of polyester of the present invention as can be seen, polyethers, polysiloxanes is the heat endurance height, and dye-uptake is good, and the polycondensation time is short.The feel of fabric also improves a lot in addition.
Claims (1)
1. a polyester, polyethers, polysiloxanes ternary copolymer fibre, it is characterized in that: component, a. contains the terephthalic acid (TPA) of a small amount of oligomer and the esterification products of ethylene glycol
B. polyethers: its general formula is HO (C
nH2
nO)
mN is 2 multiple in the H formula, and m is the multiple of 6-100, and mean molecule quantity is the 3-10% of above-mentioned esterification products weight for the 600-6000 addition
C. polysiloxanes, its general formula is
R in the formula
1, R
2, R
3, R
4Be methyl, ethyl or phenyl, m is the integer of 3-10, and mean molecule quantity is 200-1500.Addition is the 2-5% of above-mentioned esterification products weight.
D. composite thermal stabilizer:
(1) position phenol resistance anti-oxidant: addition is the 0.018-0.036% of esterification products weight
(2) phosphoric acid, phosphorous acid or its ester class, addition is the 0.008-0.04% of esterification products weight
(3) divalent metal cobalt compound, its general formula are CoCl
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108718 CN1035022C (en) | 1992-07-28 | 1992-07-28 | Ternary copolymer fibre with polyester, polyether and polyorganosiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108718 CN1035022C (en) | 1992-07-28 | 1992-07-28 | Ternary copolymer fibre with polyester, polyether and polyorganosiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069086A CN1069086A (en) | 1993-02-17 |
| CN1035022C true CN1035022C (en) | 1997-05-28 |
Family
ID=4943775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92108718 Expired - Fee Related CN1035022C (en) | 1992-07-28 | 1992-07-28 | Ternary copolymer fibre with polyester, polyether and polyorganosiloxane |
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|---|---|
| CN (1) | CN1035022C (en) |
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| JP4595437B2 (en) * | 2004-08-12 | 2010-12-08 | 富士ゼロックス株式会社 | Flame retardant biodegradable material and method for producing the same, flame retardant biodegradable polymer composition, molded article and method for disposal thereof |
| CN102031697B (en) * | 2010-11-05 | 2012-02-08 | 辽宁科隆精细化工股份有限公司 | Method for preparing polyester, polyether and modified silicone oil ternary copolymer textile finishing agent |
| CN107938368B (en) * | 2017-11-03 | 2019-05-31 | 江苏尚科聚合新材料有限公司 | A kind of low temperature can contaminate the preparation method of high-wearing feature artificial leather |
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- 1992-07-28 CN CN 92108718 patent/CN1035022C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1069086A (en) | 1993-02-17 |
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