CN102199336A - Hydrolysis-resisting fire-retardant polyester and production method thereof as well as film prepared by using polyester - Google Patents
Hydrolysis-resisting fire-retardant polyester and production method thereof as well as film prepared by using polyester Download PDFInfo
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- CN102199336A CN102199336A CN201010158187XA CN201010158187A CN102199336A CN 102199336 A CN102199336 A CN 102199336A CN 201010158187X A CN201010158187X A CN 201010158187XA CN 201010158187 A CN201010158187 A CN 201010158187A CN 102199336 A CN102199336 A CN 102199336A
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Abstract
The invention discloses hydrolysis-resisting fire-retardant polyester and a production method thereof as well as a film prepared by using the polyester. The hydrolysis-resisting fire-retardant polyester comprises at least one compound A, at least one compound B and at least one compound C, wherein the at least one compound A is selected from phosphorus compound stabilizers, the at least one compound B is selected from benzoate compounds, and the at least one compound C is selected from phosphorus-containing reaction type fire-retardant agents. The polyester and the film prepared by the polyester have the advantages of good hydrolysis resistance and good fire retardance.
Description
Technical field
The present invention relates to a kind of polyester and production method thereof and the made film of this polyester.
Background technology
Itself has excellent characteristic polyester, polyethylene terephthalate (PET) particularly, because its machinery, physics, chemical property excellence,, chemical-resistant reagent good, heat-resisting as physical strength, transparent good characteristics are widely used as fiber, film, resin and other layered products in various fields.Yet,, limited its utilization in fields such as electrical apparatus insulation material, motors because polyester self does not have flame retardant property.
In order to obtain the good polyester product of safety performance, the polyester that the numerous and confused exploitation of each company has flame retardant properties.The flame-retarded technology that uses mainly contains post-treatment technology, copolymerization, blending technology etc. at present.The post-treatment technology is mainly carried out coating processing etc. to polyester product, but has a unabiding shortcoming of flame retardant effect, and aspects such as the dyeability of product, feel are produced a lot of influences.
Chinese patent 02817032.6 adopts the method for blend to obtain fire-retardant PET, is to use brominated based flame retardant, though reached flame retardant properties, brominated flame-retardant can produce toxic smog in combustion processes, banned use of by many countries gradually.Other companies also adopt non-halogen fire retardant to be used for blend, but blending technology is that the polyester of producing is carried out secondary processing, need extra production to product to increase cost.
Each company also develops the copolymerization flame-retarded technology, gives polyester good combustion-supporting performance from essential structure.It is that comonomer adds the pet reaction system in polycondensation phase that Chinese patent 00804393.0, Chinese patent 02109909.X are to use organophosphorus, thereby obtain the copoly type flame retardant polyester, but this type polyester is total to fire retardant at the fire retardant that uses as phosphoric acid ester, the existence owing to phosphoric acid ester of synthetic back polyester, make the polyester can not hydrolysis, making the processing of fiber post-treatment for polyester, particularly high temperature dyeing has brought very big difficulty.
Summary of the invention
The object of the present invention is to provide a kind of hydrolytic resistance excellence, polyester that flame retardancy is good.
Another object of the present invention is to provide a kind of strength retention height, hydrolytic resistance excellence, polyester film that flame retardancy is good.
Technical solution of the present invention:
A kind of fire-retardant polyester of hydrolysis,
(1) contain a kind of compd A at least from phosphonium stabilizer, the addition of this phosphonium stabilizer is that its phosphoric amount is 1～1000ppm with respect to the polyester gross weight;
(2) contain a kind of compd B at least from benzoate compounds, the addition of this benzoate compounds is 0.02～2.0wt% with respect to the polyester gross weight;
(3) contain a kind of Compound C at least from phosphorous response type incombustible agent, this phosphorous response type incombustible agent addition is 1～20wt% with respect to the polyester gross weight.
The fire-retardant polyester of a kind of hydrolysis of the present invention is preferably:
(1) at least also contain a kind of Compound D from inorganic antimony compounds, the addition of this inorganic antimony compounds is that its antimony element amount is 10～500ppm with respect to the polyester gross weight;
(2) at least also contain a kind of compd E from the calcium of organic acid compound, the addition of this calcium of organic acid compound is that its calcium constituent amount is 10～500ppm with respect to the polyester gross weight;
(3) at least also contain a kind of compound F 17-hydroxy-corticosterone from the organic acid lithium compound, the addition of this organic acid lithium compound is that its elemental lithium amount is 10～200ppm with respect to the polyester gross weight.
Specifically, the fire-retardant polyester of the hydrolysis among the present invention and the film made thereof can be made by following method:
(1) transesterification reaction, in this process, add inorganic antimony compounds, calcium of organic acid compound, benzoate compounds as catalyzer, transesterification reaction reach reactivity be more than 95% or 95% in, add organic acid lithium compound and P contained compound stablizer as the catalyzer in the polycondensation.
(2) polyester that makes is dried to moisture content under 100 ℃～150 ℃ conditions be 80～200ppm, behind 240～295 ℃ of twin screw extruders, promptly obtains polyester film through biaxial oriented stretch again under nitrogen protection.
The preferred nontoxic phosphorous acid ester of phosphonium stabilizer, phosphoric acid ester.This class phosphorus stabilizer agent can reduce the content of carboxyl in the reaction preferably.
Benzoate compounds is: thing is phenylformic acid trimethyl, phenylformic acid triethyl, phenylformic acid three propyl ester, phenylformic acid tri-n-butyl, anhydrous trimellitic acid 1,2-anhydride or benzene tricarboxylic acid.The compound of preferred phenylformic acid trimethyl, anhydrous trimellitic acid 1,2-anhydride can shorten the reaction times as the polyester anti-dripping agent, reduces carboxyl-content, and its addition is 0.1～0.8wt% with respect to weight polyester preferably.
Phosphorous response type incombustible agent is the compound with following general structure:
Wherein R, R ' group are hydrogen atom, methyl, ethyl, hydroxyethyl, hydroxyl normal-butyl or hydroxypropyl.
Inorganic antimony compounds is not particularly limited, and preferably inorganic antimony compounds comprises antimonous oxide, antimony peroxide etc., wherein especially preferably uses the stable antimonous oxide of catalytic.
The calcium of organic acid compound is caoxalate, calcium acetate, calcium stearate etc., and the preferred calcium of organic acid compound of the present invention is and reaction system consistency calcium acetate preferably.
The organic acid lithium compound is Lithium Acetate, butyllithium, phenyl lithium etc., and the preferred organolithium compound of the present invention is a reaction system consistency Lithium Acetate preferably.
Hydrolysis fire-retardant polyester that the present invention makes and the film of making thereof: hydrolysis index %BB≤0.5 of its hydrolysis fire-retardant polyester composition; The fire-retardant polyester film is under 155 ℃, the condition of 10%RH, 4h, and the difficult combustion of the film of making grade reaches UL94VTM-2.
Hydrolysis fire-retardant polyester that the present invention makes and the film of making thereof are not halogen-containing, anti-drippage property is excellent, anti-add water-disintegrable good, flame retardancy is good, is a kind of solar cell goods of environment-friendly novel.
Embodiment
In order to further specify the advantage more than the present invention, will be described in detail from listed examples and comparative example below.Yet the present invention has more than and is limited to following embodiment.
Below raw material and the medicine that is suitable among the present invention described:
Dimethyl terephthalate (DMT) (DMT): grade is a high purity, Iranian product;
Ethylene glycol: BASF AG's product;
Antimonous oxide: AR, Shishewei Chemical Co., Ltd., Shanghai's product;
Calcium acetate compound: AR, the Shanghai vast and boundless biochemical technology of literary composition company limited product;
Lithium Acetate compound: AR, Shanghai permanent letter chemical reagent factory product;
Phosphonium stabilizer: trimethyl phosphite 99: AR, the emerging bio tech ltd product of Shanghai section;
Benzene-1,2,4-tricarboxylic acid trimethyl (TMTM): ladder is uncommon likes that (Shanghai) changes into industrial development company limited product;
Incombustible agent (DDP): be ethylene glycol solution, Takemoto Oil and Fat's product.
Embodiment 1:
Under 140 ℃ temperature, with 194 parts of (weight) dimethyl terephthalate (DMT), the anti-dripping agent TMTM of 120 parts of (weight) ethylene glycol and 0.1wt% carries out direct transesterification reaction, The catalytic antimony trioxide 300ppm in the transesterify (content of antimony element is 250ppm), calcium acetate 900ppm (content of calcium constituent is 205ppm) (wherein addition is the addition with respect to weight polyester), transesterification reaction reach reactivity be more than 95% or 95% in, this moment, temperature of reaction system was 235 ℃, after methanol fraction distillates, add Lithium Acetate 1800ppm (content of elemental lithium is 122ppm), behind the trimethyl phosphite 99 1112ppm (content of phosphoric is 246ppm) (wherein addition is the addition with respect to weight polyester), the prepolymer that obtains.
Behind the above-mentioned prepolymer that makes, add incombustible agent 2wt%DDP.Precondensation 45～60min under rough vacuum carries out polycondensation under the high vacuum more then, and vacuum tightness is below the 200Pa, and temperature of reaction is 220 ℃～320 ℃, preferred 250 ℃ ~ 300 ℃.When polymer viscosity reached 0.55～0.75, polycondensation finished, and makes the section of the fire-retardant polyester PET of hydrolysis.
The viscosity of gained PET (IV) is 0.611dl/g, and the tone L value of polyester slice is 62.1, and the b value is 4.5.COOH content 11.2eq/t before the polyester hydrolysis treatment.The foreign matter observations is: the foreign matter number of 1～8 μ m is 9, is 2 greater than 8 μ m.
The PET section that makes; under 100 ℃～150 ℃ conditions, be dried to moisture and reach 80～200ppm, promptly obtain fire retardant mylar at the nitrogen protection biaxial oriented stretch; measuring its BB% through hydrolysis treatment (155 degree saturated vapor pressures were handled 4 hours) back is 0.31.
Embodiment 2
Experiment condition is with embodiment 1,
The addition of TMTM is: 0.3wt%.
Embodiment 3
Experiment condition is with embodiment 1,
The addition of incombustible agent DDP is: 3wt%,
The addition of TMTM is: 0.5wt%.
Embodiment 4
Experiment condition is with embodiment 1,
The addition of incombustible agent DDP is: 5wt%,
The addition of TMTM is: 1.0wt%.
Embodiment 5
Experiment condition is with embodiment 1,
The addition of incombustible agent DDP is: 10wt%,
The addition of TMTM is: 0.5wt%.
Embodiment 6
Experiment condition is with embodiment 1,
The addition of incombustible agent DDP is: 15wt%,
The addition of TMTM is: 0.5wt%.
Comparative example 1
Experiment condition is with embodiment 1,
The addition of DDP is 0wt%,
The consumption of TMTM is 0.5wt%.
Comparative example 2
Experiment condition is with embodiment 1,
The addition of DDP is 10wt%,
The consumption of TMTM is 0wt%.
Comparative example 3
Experiment condition is with embodiment 1,
The addition of DDP is 30wt%,
The consumption of TMTM is 0.5wt%.
The physicals of the polyester for preparing in embodiment and comparative example is listed in the table one.
As can be seen, polyester terminal carboxyl(group) value can increase behind the adding fire retardant from embodiment and comparative example, but after adding benzoic ether and inorganic phosphate, polyester terminal carboxyl(group) value obviously reduces, and the %BB value also obviously reduces.And after in reaction system, adding benzoic ether, when difficult combustion is estimated drip phenomenon be improved significantly.
Among the present invention, we mainly investigate the carboxyl value of polyester slice, the difficulty combustion rank of %BB and polyester film, drippage situation, the foreign matter situation of strength retention and film is so fire retardant, phenylformic acid, inorganic phosphate three's addition all needs the attribute of comprehensive polyester slice and polyester film to consider.
Though presented for purpose of illustration the property purpose the preferred embodiments of the invention are disclosed, those of ordinary skills can understand in not breaking away from the scope and spirit of the present invention of claim, available various modifications, adding and substitute.
The following describes the measuring method and the evaluation method of the every index of the present invention.
(1) limiting viscosity (IV) (dL/g)
The polyester of 1.6 grams is dissolved in the ortho chloro phenol solution of 20ml, measures its limiting viscosity (IV) down at 25 ℃.
(2) carboxyl-content (COOH)
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N then.
(3) tone L, b value
Measure by GB GB/T 14190-1993.
(4) hydrolytic resistance index %BB
Get the hydrolysis system for handling that a certain amount of polyester granules places sealing, under 155 ℃, 100% humidity, handle 4h, measure its limiting viscosity behind the sample drying after handling then, the polyester slice viscosity change is reflected at the variation of the %BB of polyester slice before and after the comparison process.
％BB＝0.27×([IV
1]
-4/3-[IV
0]
-4/3)
In the equation, IV
0Represent the limiting viscosity of the preceding polyester of hydrolysis treatment, IV
1Represent the limiting viscosity of polyester after the hydrolysis treatment.
(5) observation of foreign matter
The 5mg polyester slice is placed on cover glass (18mm is square), 260 ℃ of following heating and meltings, treat its fusing after attached again a slice cover glass, carry out compressing tablet.At OLYMPUS BX51, under the pattern of darkroom, 400 times of magnifications are observed foreign matter.Move horizontally (microscope), observe the full surface of sample, Tong Ji diameter is the foreign matter number of 1～8 μ m simultaneously.
(6) flame retardant resistance test evaluation
Estimate according to the thin fire-retardant judgement criteria of matter of U.S. UL94-VTM.
(7) judgement of dropping
In thin material UL94-VTM test, observing when burning is estimated has the thing dropping to generate.
Claims (6)
1. hydrolysis fire-retardant polyester is characterized in that:
(1) contain a kind of compd A at least from phosphonium stabilizer, the addition of this phosphonium stabilizer is 0.001～1wt% with respect to the polyester gross weight;
(2) contain a kind of compd B at least from the benzoic acid derivative that contains three substituted radicals on the phenyl ring, the addition of this benzoic acid derivative is 0.02～2.0wt% with respect to the polyester gross weight;
(3) contain a kind of Compound C at least from phosphorous response type incombustible agent, this phosphorous response type incombustible agent addition is 1～20wt% with respect to the polyester gross weight.
2. hydrolysis fire-retardant polyester according to claim 1 is characterized in that:
(1) at least also contain a kind of Compound D from inorganic antimony compounds, the addition of this inorganic antimony compounds is that its antimony element amount is 10～500ppm with respect to the polyester gross weight;
(2) at least also contain a kind of compd E from the calcium of organic acid compound, the addition of this calcium of organic acid compound is that its calcium constituent amount is 10～500ppm with respect to the polyester gross weight;
(3) at least also contain a kind of compound F 17-hydroxy-corticosterone from the organic acid lithium compound, the addition of this organic acid lithium compound is that its elemental lithium amount is 10～200ppm with respect to the polyester gross weight.
3. the production method of the described hydrolysis fire-retardant polyester of claim 1 is characterized in that: carry out transesterify or esterification obtains the small molecules polymkeric substance by the benzoic acid derivative that three substituted radicals are arranged on aromatic binary carboxylic acid ester, the pure and mild phenyl ring of binary aliphatic; Before transesterification reaction, add inorganic antimony compounds, calcium of organic acid compound as catalyzer; After transesterify or esterification, add organic acid lithium compound and phosphonium stabilizer as the catalyzer in the polycondensation.
4. the production method of hydrolysis fire-retardant polyester according to claim 3 is characterized in that: the benzoic acid derivative that contains three substituted radicals on the phenyl ring is phenylformic acid trimethyl, phenylformic acid triethyl, phenylformic acid three propyl ester, phenylformic acid tri-n-butyl, anhydrous trimellitic acid 1,2-anhydride or benzene tricarboxylic acid.
5. the production method of hydrolysis fire-retardant polyester according to claim 3 is characterized in that: the chemical general formula of phosphorous response type incombustible agent is as follows:
Wherein R, R ' group are hydrogen atom, methyl, ethyl, hydroxyethyl, hydroxyl normal-butyl or hydroxypropyl.
6. made film of the described hydrolysis fire-retardant polyester of claim 1 is characterized in that: under 155 ℃, the condition of 100%RH, 4h, and hydrolysis index %BB≤0.5 of polyester slice; The difficulty combustion grade of making film is UL94VTM-2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
| CN101469108A (en) * | 2007-12-24 | 2009-07-01 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
| CN101469108A (en) * | 2007-12-24 | 2009-07-01 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
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Application publication date: 20110928 |