CN104245789A - Method for producing flame-retardant polyester, and flame-retardant master batch - Google Patents
Method for producing flame-retardant polyester, and flame-retardant master batch Download PDFInfo
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- CN104245789A CN104245789A CN201380016178.9A CN201380016178A CN104245789A CN 104245789 A CN104245789 A CN 104245789A CN 201380016178 A CN201380016178 A CN 201380016178A CN 104245789 A CN104245789 A CN 104245789A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Abstract
Provided is a method for producing a flame-retardant polyester which contains phosphorous at a high concentration through copolymerization, has a high degree of polymerization, a low degree of copolymerization of a diethylene glycol component, and rarely undergoes discoloration. A method for producing a flame-retardant polyester, comprising a step of agitating a composition comprising components (A) to (E) mentioned below while heating: (A): a phosphorous compound represented by general formula (1); (B): an unsaturated dicarboxylic acid or an ester-forming derivative thereof; (C): a saturated aliphatic polyhydric alcohol mainly composed of ethylene glycol and/or an ester-forming derivative thereof; (D): a polycarboxylic acid other than the component (B) or an ester-forming derivative thereof; and (E): an acetic acid metal salt.
Description
Technical field
The present invention relates to the manufacture method of the fire-retardant polyester containing high concentration phosphorus.Fire-retardant polyester according to the inventive method gained can be used as fire-retardant master batch.
Background technology
Our known organic compound (following, this compound is called DOP) by taking 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as representative and polyethylene terephthalate copolymer, can containing high concentration phosphorus and the fire retardant not easily moved.In addition, we known with phosphorus compound copolymerization such as DOP after the high copolyester of phosphorus content as fire-retardant master batch, in thermoplastic resin (matrix resin), the fire-retardant master batch of mixing, carries out melting mixing, gives the technology (referenced patent document 1) of its flame retardant resistance.
As the manufacture method of the polyester manufactured and after phosphorus compound copolymerization, we are known except using the pre-synthesis method (referenced patent document 1) with the phosphorus compound of ester forming, also have the method (referenced patent document 2, patent documentation 3) using and do not have the specific phosphorus compound of ester forming.
In patent documentation 2, disclose the manufacture method of the fire-retardant polyester of specific phosphorus compound and the specific unsaturated fatty acids compounds of group adding specified quantitative before esterification or esterification.In addition, in patent documentation 3, disclose in the reaction system of esterification or transesterification reaction, make specific phosphorus compound, specific unsaturated carboxylic acid or its ester-forming derivatives, fire line polyester System making method that specific aminate coexists.As according to these class methods, then without the need to other approach manufacture can with the ester forming phosphorus compound of polyethylene terephthalate copolymer, so we think that the manufacturing cost significantly reducing fire-retardant polyester is possible.
Look-ahead technique document
Patent documentation
Patent documentation 1: Japanese Patent No. 3934133 publication
Patent documentation 2: Japanese Patent Laid-Open 2000-212266 publication
Patent documentation 3: Japanese Patent No. 4006629 publication
Summary of the invention
But, after present inventors studied the vibrin of the high concentration phosphorus being contained more than 30000ppm according to the method manufacture described in patent documentation 2 and patent documentation 3 by copolymerization, phosphorus compound makes polymerizing catalyst inactivation and is difficult to obtain the vibrin of high-polymerization degree, the second-order transition temperature decline of the glycol ether copolymerization that in polymerization process, side reaction generates and the vibrin that obtain, and aminate causes vibrin generation painted, has understood fully the generation of this type of phenomenon.And, if use using the fire-retardant polyester producing this type of phenomenon as fire-retardant master batch, then the mechanical properties such as flexural strength, modulus in flexure, tensile yield strength, flecxure temperature of fire-retardant master batch and the molten mixture of matrix resin is compared to decline significantly and have with matrix resin and painted tendency is occurred, and has known clearly to have problems in the purposes requiring the mechanical properties of height or less colored or non-coloring.
In view of the foregoing, the object of the present invention is to provide the manufacture method of fire-retardant polyester, though this fire-retardant polyester is by copolymerization containing the fire-retardant polyester of high concentration phosphorus, high and the low and painted few fire-retardant polyester of copolymerization ratios that is glycol ether composition of the polymerization degree simultaneously.
The present inventor etc. for complete above-mentioned problem make great efforts research after, find in polycarboxylic acid or its ester-forming derivatives and saturated fatty dibasic alcohol or its ester-forming derivatives, by making specific phosphorus compound, unsaturated carboxylic acid or its ester-forming derivatives, and metal acetate salt coexist heating mixing, can manufacture at a low price by copolymerization containing high concentration phosphorus, simultaneously high and the low and painted few fire-retardant polyester of copolymerization ratios that is glycol ether composition of the polymerization degree, so complete the present invention.
That is, the present invention is as described below.
<1>
The manufacture method of fire-retardant polyester, it possesses the composition operation of heating mixing containing following (A) ~ (E) composition,
(A) composition: the phosphorus compound of following general formula (1),
[changing 1]
(B) composition: unsaturated dicarboxylic acid or its ester-forming derivatives,
(C) composition: the representative examples of saturated aliphatic polyvalent alcohol being main formation with ethylene glycol and/or ester-forming derivatives,
(D) composition: the polycarboxylic acid beyond (B) composition or its ester-forming derivatives,
(E) composition: metal acetate salt.
<2>
The manufacture method of fire-retardant polyester, it possesses heating mixing containing the operation (P) of the composition of following (A) ~ (E) composition, by adding (F) composition in the composition of operation (P) gained: the operation (Q) then heating decompression after polymerizing catalyst
(A) composition: the phosphorus compound of following general formula (1),
[changing 2]
(B) composition: unsaturated dicarboxylic acid or its ester-forming derivatives,
(C) composition: the representative examples of saturated aliphatic polyvalent alcohol being main formation with ethylene glycol and/or ester-forming derivatives,
(D) composition: the polycarboxylic acid beyond (B) composition or its ester-forming derivatives,
(E) composition: metal acetate salt.
<3>
The manufacture method of the fire-retardant polyester according to <1> or <2>, wherein, (B) composition is toxilic acid, fumaric acid and/or methylene-succinic acid.
<4>
Fire-retardant master batch, it contains fire-retardant polyester and metal acetate salt; Described fire-retardant polyester, with the total 200 % by mole of the whole polyacid constituent and whole polyhydroxy reactant that form this fire-retardant polyester for benchmark, by the di-carboxylic acid composition with the organic group represented by following general formula (2) of 20 ~ 60%, with polycarboxylic acid the composition more than ternary adding up to 0.05 ~ 3 % by mole and/or polyhydroxy reactant more than ternary, with the aromatic binary carboxylic acid composition of 37 ~ 79.95 % by mole, and the fire-retardant polyester that remaining aliphatic dihydroxy alcohol composition is formed; The Co-b value of fire-retardant master batch is-5 ~ 20, Co-L value is more than 50,
[changing 3]
<5>
Fire-retardant master batch according to <4>, wherein, the copolymerization ratios forming the glycol ether composition of described flame-retardant polyester resin is less than 30 % by mole.
According to the present invention, can produce by copolymerization containing the phosphorus of high density at a low price, simultaneously high-polymerization degree and the low and painted few fire-retardant polyester of the copolymerization ratios of glycol ether composition.In addition, by using the fire-retardant polyester by manufacture method gained of the present invention as fire-retardant master batch use, the mechanical properties of matrix resin can not be damaged and the high fire-retardant thermoplastic resin composite of painted few transparency.
Embodiment
Below, in further detail the present invention is described.
The present invention relates to the manufacture method of fire-retardant polyester, possess heating mixing to contain: (A) composition: the phosphorus compound of general formula (1), (B) composition: unsaturated dicarboxylic acid or its ester-forming derivatives, (C) composition: representative examples of saturated aliphatic dibasic alcohol or its ester-forming derivatives, (D) composition: the polycarboxylic acid beyond (B) composition or its ester-forming derivatives, (E) composition: the operation (P) of the composition of metal acetate salt.In addition, relate to the manufacture method of fire-retardant polyester, possessing the operation (Q) then heating decompression by adding (F) composition polymerizing catalyst in the composition of operation (P) gained.Fire-retardant polyester of the present invention is the multipolymer of (A) composition (B) composition affixture, (C) composition and (D) composition.
In the manufacture method of fire-retardant polyester of the present invention, the phosphorus compound of (A) composition general formula (1), (B) composition unsaturated carboxylic acid or its ester-forming derivatives and (E) multicomponent metallic acetate must be made, coexisted before esterification or transesterification reaction.Because through this operation, (A) composition and being swift in response of (B) composition are carried out, even if esterification and/or transesterification reaction are carried out under high temperature condition of high vacuum degree, the initial stage of reaction also promptly can stablize ester forming phosphorus compound derivative by Heat of Formation, so the crosslinked and adjoint gelation that can suppress the decline of the copolymerization ratios caused due to the volatilization of (A) composition and be formed due to the reaction of (B) composition
In addition, (F) composition polymerizing catalyst is added after preferred esterification and transesterification reaction.By adding (F) composition in this step of reaction, (A) composition phosphorus compound can not make (F) composition polymerizing catalyst inactivation, and has the tendency that stably can manufacture the polyester of more high-polymerization degree.
The phosphorus compound of (A) used in the present invention composition general formula (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOP).DOP has the effect of giving polyester fire line, but because itself not having into the ability of ester, so to one-tenth ester reaction torpescence, the polymeric composition of polyester directly can not be it can be used as.Therefore, in the present invention, in the manufacturing process of polyester, when carrying out esterification or transesterification reaction, in reaction system, DOP and unsaturated carboxylic acid or its ester-forming derivatives are coexisted, make it generate heat-staple ester forming phosphorus compound derivative, made ester forming phosphorus compound derivative and the polyethylene terephthalate copolymer of this generation by polycondensation operation, be manufactured on the fire-retardant polyester containing DOP residue in side chain.In addition, in the present invention, from raw materials cost preferably through the direct esterification of esterification.
As (B) used in the present invention composition unsaturated carboxylic acid or its ester-forming derivatives, can be exemplified as, the unsaturated monocarboxylics such as vinylformic acid, butenoic acid, methacrylic acid, the unsaturated dicarboxylic acids such as toxilic acid, fumaric acid, methylfumaric acid, citraconic acid, methylene-succinic acid, the acid anhydrides such as alkyl ester, maleic anhydride, citraconic anhydride, itaconic anhydride of the methyl esters of aforementioned unsaturated carboxylic acid or ethyl ester etc.In the middle of these preferably, unsaturated dicarboxylic acid or its ester-forming derivatives such as toxilic acid, fumaric acid and methylene-succinic acid.No matter these compounds are used alone any one or and all can with both are above.
In the manufacture method of fire-retardant polyester of the present invention, (A) phosphorus compound of composition general formula (1) and (B) composition unsaturated carboxylic acid or its ester-forming derivatives, preferably, the use of first-class mole of essence, but whichsoever can in the scope of positive and negative 20 % by mole taking equimolar amount as benchmark.But, once (A) composition exceeds 20 % by mole of (B) composition relative to (B) composition, polymerizing catalyst inactivation, polymerization needs long-time, or has the tendency having tone variation and the muddy reason becoming polyester owing to not having the catalyzer of activation.On the contrary, once 20 % by mole of (A) composition more than (B) composition fewer than (B) composition, the amount of unsaturated carboxylic acid is superfluous, has the tendency of gelation or the painted reason becoming polyester.That is, in the present invention, (A) composition and (B) composition content separately, its no matter which side, preferable range is 80 ~ 120 % by mole of any the opposing party, and particularly preferably, scope is 85 ~ 115 % by mole.
In fire-retardant polyester of the present invention, preferred copolymerization has the di-carboxylic acid composition with the organic group represented by general formula (2) as (A) composition of 20 ~ 60 % by mole.The copolymerization ratios with the di-carboxylic acid composition of the organic group represented by general formula (2) is discontented with 20 % by mole, the blending ratio of fire-retardant master batch relative to matrix resin must be improved to give full play to flame retardant effect, therefore the mechanical properties of mixture may be caused more far short of what is expected than the mechanical properties of matrix resin, and this is that we are undesirable.In addition, there is the copolymerization ratios of the di-carboxylic acid composition of the organic group represented by general formula (2) higher than 60 % by mole, there is the tendency of the reason becoming the flame-retarded resin being difficult to obtain high-polymerization degree, therefore the mechanical properties of mixture may be caused more far short of what is expected than the mechanical properties of matrix resin, and this is that we are undesirable.
(D) of the present invention composition, it is polycarboxylic acid beyond (B) composition or its derivative.Preferably (D) composition formed primarily of aromatic binary carboxylic acid or their ester-forming derivatives.As aromatic binary carboxylic acid composition, can be exemplified as, terephthalic acid, 1, 3-naphthalene dicarboxylic acids, 1, 4-naphthalene dicarboxylic acids, 1, 5-naphthalene dicarboxylic acids, 2, 6-naphthalene monocarboxylic acid, 2, 7-naphthalene dicarboxylic acids, phthalic acid, m-phthalic acid, 5-(basic metal) sulfoisophthalic acid, diphenic acid, 4, 4'-diphenyl dicarboxylic acid, 4, 4'-Dicarboxy diphenylsulfone, 4, 4'-dicarboxydiphenyl ether, 1, 2-phenoxy group ethane-p, p'-dicarboxylic acid, aromatic binary carboxylic acid and the ester-forming derivatives thereof such as anthracene dicarboxylic acid, in these aromatic binary carboxylic acids, preferred terephthalic acid, 2, 6-naphthalene dicarboxylic carboxylic acid.
(C) of the present invention composition is it take ethylene glycol as representative examples of saturated aliphatic polyvalent alcohol and/or the ester-forming derivatives of main composition.For (C) composition, can be exemplified as, ethylene glycol, 1, 2-propylene glycol, 1, ammediol, Diethylene Glycol, triglycol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 2, 3-butyleneglycol, 1, 4-butyleneglycol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexylene glycol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1, 4-hexanaphthene di-alcohol, 1, 10-decanediol, 1, 12-dodecanediol, polyoxyethylene glycol, polypropylene glycol, the aliphatic diols such as polytetramethylene ether diol, in these glycol, the second-order transition temperature (Tg) improving fire-retardant polyester preferably, ethylene glycol, 1, ammediol, 1, 4-butyleneglycol, the carbonatomss such as neopentyl glycol are the glycol of 2 ~ 5, preferably main, ethylene glycol is more than 50 % by mole.
In addition, in fire-retardant polyester of the present invention, the viscosity improving fire-retardant polyester preferably, copolymerization has the polyfunctional group composition of more than the trifunctionals such as the alcohol of more than the ternary such as carboxylic acid, glycerol, TriMethylolPropane(TMP), tetramethylolmethane of more than the ternarys such as trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid, particularly with the total 200 % by mole of the whole polyacid constituent and whole polyhydroxy reactant that form this fire-retardant polyester for benchmark, preferred copolymerization has the polyvalent alcohol of more than the polycarboxylic acid composition of more than the ternary adding up to 0.05 ~ 3 % by mole and/or ternary.The total amount of polycarboxylic acid and/or polyvalent alcohol is discontented with 0.05 % by mole, is difficult to improve the polymerization degree and reaches target viscosities.More than 3 % by mole, the side chain of polyester is superfluous, may produce gelation.Preferably, the total amount of polycarboxylic acid and/or polyvalent alcohol is 0.05 ~ 3 % by mole, and further preferably, it is 0.1 ~ 2 % by mole.
Preferably, (E) of the present invention multicomponent metallic acetate is alkali metal acetate, Alkaline Earth Metal Acetate, transition metal acetate etc., in the middle of, from the tone suppressing polyester preferably, sodium-acetate, Lithium Acetate, Cobaltous diacetate etc.Mixing sodium-acetate, preferably mixing take fire-retardant polyester as the sodium atom of benchmark is the sodium-acetate of 5 ~ 50ppm, is more preferably 10ppm ~ 30ppm.Below 5ppm, it has the tendency of the effect reducing the copolymerization ratios suppressing Diethylene Glycol composition.In addition, the words of more than 50ppm have the tendency strengthening coloring resin.In addition, in order to reduce the Co-b value of fire-retardant master batch, preferably mixing cobalt atom is the Cobaltous diacetate of 5 ~ 50ppm, further preferred 10ppm ~ 30ppm.The effect of the words reduction Co-b value of below 5ppm is not high.And the words resin blueness of more than 50ppm strengthens.
(F) of the present invention composition polymerizing catalyst, though be not particularly limited, if catalyzer such as use germanium compound, aluminum compound etc., there is the effect suppressing fire-retardant polyester melanism, have the tendency of the polyester obtaining high Co-L value, thus preferably.Preferred germanide especially from polymerization activity height.
In the manufacture method of fire-retardant polyester of the present invention, esterification or the front metal acetate salt added in reaction system of transesterification reaction, even if still have residual in polycondensation step.Make reaction system become weakly alkaline because of the residual of metal acetate salt, inhibit the generation of the side reaction of Diethylene Glycol.By this type of interaction energy, Diethylene Glycol is controlled lower relative to the copolymerization ratios of fire-retardant polyester, play this type of effect.Preferably, the Diethylene Glycol composition formed in the aliphatic polyol composition of fire-retardant polyester of the present invention is less than 30 % by mole.If the copolymerization ratios of Diethylene Glycol composition uprises, have the tendency of the Tg value step-down of fire-retardant polyester, more than 30 % by mole, probably can cause mechanical properties low and dry time adhesion (Blocking).
Fire-retardant master batch of the present invention must contain fire-retardant polyester of the present invention and metal acetate salt, but also can mix other resin, phase solvation and/or various additive.Such as, by using pigment or antioxidant used in combination as additive, anti-painted and oxidation resistant effect can be added on fire-retardant master batch.In addition, according to other resins high with matrix resin consistency used in combination or phase solvation, can expect to obtain the effects such as the simplification of melting mixing operation or fire-proof resin composition homogenization.
Preferably, the water content of fire-retardant master batch of the present invention is less than 0.1 % by weight, more preferably less than 0.05 % by weight, be further preferably less than 0.03 % by weight.Water content be less than 0.1 % by weight can be fully dry, have the tendency suppressing adhesion or decomposition.
Mix fire-retardant master batch of the present invention and thermoplastic resin (matrix resin), the fire-retardant thermoplastic resin composite of the phosphorus containing specified amount can be manufactured.
Fire-retardant master batch of the present invention, preferably, measuring L value (whiteness) by hunter colour-difference meter is more than 50, is preferably more than 55 further.And preferably, the b value measured by hunter colour-difference meter for more than-5 less than 20, further preferably less than 15, less than 10.By taking the manufacture method of fire-retardant polyester of the present invention, the high and fire-retardant master batch of lurid less colored or non-coloring of whiteness can be obtained.In addition, it is less painted and coloring resistance is good for fire-retardant master batch of the present invention.Therefore, the whiteness mixing the thermoplastic resin composition that fire-retardant master batch of the present invention obtains in matrix resin is much the same with the common matrix resin before the fire-retardant master batch of mixing.
Fire-retardant master batch, relative to the blending ratio of matrix resin, can suitably adjust by the phosphorus content desired by mixed flame resistance thermoplastic resin compositions, usually, is preferably 0.5 ~ 90 % by weight of flame resistance thermoplastic resin compositions.More preferably 1 ~ 50 % by weight, be further preferably 10 ~ 30 % by weight.Though the phosphorus content in fire-retardant thermoplastic resin composite is not particularly limited, from flame retardant resistance, at more than 1000ppm, further more than 2000ppm, further more than 4000ppm's is effective.In the prior art, as fire-retardant master batch owing to can not meet high phosphorus concentration, high-polymerization degree and high second-order transition temperature simultaneously, or the weakened of products formed due to the forming process of the flame resistance thermoplastic resin compositions of the phosphorus content that meets aforementioned range, or because the necessary cooling time of taking out products formed from mould is elongated, thus impracticable, but easily can produce the products formed with sufficient intensity with efficient production efficiency in the present invention.
As the matrix resin mixed by fire-retardant master batch of the present invention, arbitrary thermoplastic resin can be used.For arbitrary thermoplastic resin, can be exemplified as, polyolefin resin, polystyrene resin, acronitrile-butadiene-styrene copolymer resins, vinyl cyanide styrene copolymerized resin, (methyl) acrylic resin styrene copolymerized resin, (methyl) acrylic resin, butadiene styrene copolymer resins, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin, polyallyl sulphone resin, polyethersulfone resin, polyetherimide resin, polyimide resin, polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate), the vibrin such as poly(lactic acid), polyestercarbonate resins, polyester ether resin, urethane resin and their resin alloy etc., when being particularly applicable to vibrin, in consistency preferably.
Embodiment
Specifically describe the present invention for embodiment below, but the present invention is not limited only to embodiment.In addition, each test in this specification sheets is carried out according to following methods.
(1) phosphorus concentration: take sample resin 7g with miniature electric balance.After iron plate uses face (minute surface) has discharged aluminum dish, in the middle of put into load weighted sample.The iron plate of placing sample is put into the hot-air drier of 270 DEG C, thermal treatment 20 minutes.After cooling, from each aluminum dish iron plate, separate the sample of melting, obtain the thick sample board reaching about 5mm.The noncontact iron plate side of x-ray fluorescence analyzer system 3270 pairs of sample boards of Rigaku society is used to carry out x-ray fluorescence analysis, quantitative phosphorus concentration.
(2) limiting viscosity: the limiting viscosity of sample, measures under phenol/sym.-tetrachloroethane mixing solutions (weight ratio (3/2)), the condition of 30 DEG C.
(3) colourimetric number: the colourimetric number of sample, it is measured by hunter colour-difference meter.Co-L value larger expression whiteness is stronger, and Co-b value larger expression yellowing is stronger.
(4) second-order transition temperature (Tg): use differential scanning calorimeter (DSC), 200 DEG C are risen to from room temperature with the heat-up rate of 20 DEG C/minute, after cooling rapidly with liquid nitrogen, 200 DEG C are warming up to from 0 DEG C again, the intersection point of the tangent line of establishment of base line and flex point with the heat-up rate of every 20 DEG C/minute.Aluminium gland type container sample 5mg put into by sample, curling pressure-like and using.
(5) polymerization time
Time that 0.67 (target value) ± 0.03dl/g spends is risen to for polymerization time to the limiting viscosity (IV) of polyester during to drop to 10hPa from pressure in retort in polycondensation step.But, be higher limit computation and measurement with 240 minutes.
(6) granulation processing method
After polycondensation step terminates, from metal mouth, discharge the polyester of molten state by nitrogen pressurization, wire harness shape extrude, put into fill with have the water coolant of the tank of water coolant after, granulate with wire harness cutting knife.Obtain the class cylindrical pellet of diameter 3mm, about length 3mm.
Below, be embodiment about fire-retardant master batch polyester and resin composition of the present invention and comparative example.
(embodiment 1)
By the polyacid constituent, the phosphorus compound that represent in table 1, add according to the ratio described in table 1, the polyhydroxy reactant represented in table 1 adds with 2 molar equivalents that whole polyacid constituent is benchmark, is warming up to 240 DEG C, carries out esterification under pressurized state.Germanium dioxide in this reactant of esterification is that the germanium atom conversion of benchmark adds 200ppm with resin, transfers them to polycondensation tank, gradually reduces pressure and drop to below 1.3hPa after 60 minutes in 60 minutes while being warming up to 265 DEG C.Polycondensation is carried out while stirring until arrive the target limit viscosity (0.67 ± 0.03dl/g) of polyester with this condition, must containing the polyester of phosphorus atom.
(embodiment 2,3)
By in table 1 represent compound, according in table 1 represent ratio, manufacture identical with embodiment 1 and polyester.
(embodiment 4)
Except sodium-acetate compound is become except Cobaltous diacetate, manufacture identical with embodiment 1 and polyester.
(comparative example 1)
Except do not add sodium-acetate reaction except, manufacture identical with embodiment 1 and polyester.But the Tg value of gained polyester is low, during drying temperature 60 DEG C, can there is the adhesion of particle in confirmation.
(comparative example 2)
Become except Tributylamine except by sodium-acetate, manufacture identical with embodiment 1 and polyester.But polycondensation does not reach the limiting viscosity of target, the painted of gained resin also can worsen.
As indicated in table 1, embodiment 1 ~ 4, can manufacture the phosphorus atom content containing the abundance obtaining excellent flame retardancy, and the copolymerization ratios of Diethylene Glycol is suppressed to lower level simultaneously, be 11 ~ 20 % by mole, high-polymerization degree, high glass transition temperature and painted repressed fire-retardant polyester.And comparative example 1 does not use acetate, the copolymerization ratios of Diethylene Glycol shared by the fire-retardant polyester of gained is higher, is 34 % by mole.The second-order transition temperature step-down of the polyester of gained, there occurs the adhesion in drying process thus.In addition, comparative example 2 does not use acetate and adds Tributylamine, although the copolymerization ratios of Diethylene Glycol is suppressed to lower level, is 15 % by mole, but the inactivation of the polymerizing catalyst that Tributylamine can partly cause, even if the fire-retardant polyester extending that polymerization time can not manufacture high-polymerization degree.In addition, occur painted in the fire-retardant polyester of gained because of Tributylamine.
Industrial utilizability
According to the manufacture method of fire-retardant polyester of the present invention, painted minimizing can be obtained, the fire-retardant polyester of mechanical properties excellence.Fire-retardant polyester of the present invention can be used as the flame-retardant composition mixed in fire-retardant master batch, by mixing fire-retardant master batch of the present invention in arbitrary thermoplastic resin (matrix resin), carry out melting mixing, the low of painted and mechanical properties can be suppressed, can fire-retardant thermoplastic resin composite be obtained.The fire-retardant thermoplastic resin composite of gained, by extrusion molding, injection-molded shaping, can utilize at dress material fiber or Industrial materials fiber, film, engineering plastics or sizing agent etc.
Claims (5)
1. the manufacture method of fire-retardant polyester, it possesses the operation of heating mixing containing the composition of following (A) ~ (E) composition,
(A) composition: the phosphorus compound of following general formula (1),
[changing 1]
(B) composition: unsaturated dicarboxylic acid or its ester-forming derivatives,
(C) composition: the representative examples of saturated aliphatic polyvalent alcohol being main formation with ethylene glycol and/or ester-forming derivatives,
(D) composition: the polycarboxylic acid beyond (B) composition or its ester-forming derivatives,
(E) composition: metal acetate salt.
2. the manufacture method of fire-retardant polyester, it possess heating mixing containing the composition of following (A) ~ (E) composition operation (P), in the composition obtained by operation (P), add (F) composition: the operation (Q) then heating decompression after polymerizing catalyst
(A) composition: the phosphorus compound of following general formula (1),
[changing 2]
(B) composition: unsaturated dicarboxylic acid or its ester-forming derivatives,
(C) composition: the representative examples of saturated aliphatic polyvalent alcohol being main formation with ethylene glycol and/or ester-forming derivatives,
(D) composition: the polycarboxylic acid beyond (B) composition or its ester-forming derivatives,
(E) composition: metal acetate salt.
3. the manufacture method of the fire-retardant polyester according to claims 1 or 2, wherein, (B) composition is toxilic acid, fumaric acid and/or methylene-succinic acid.
4. fire-retardant master batch, it contains fire-retardant polyester and metal acetate salt, it is characterized in that, described fire-retardant polyester, its with the total 200 % by mole of the whole polyacid constituent and whole polyhydroxy reactant that form this fire-retardant polyester for benchmark, by the di-carboxylic acid composition with the organic group represented by following general formula (2) of 20 ~ 60%, add up to the polyhydroxy reactant of more than the polycarboxylic acid composition of more than the ternary of 0.05 ~ 3 % by mole and/or ternary, the fire-retardant polyester that the aromatic binary carboxylic acid composition of 37 ~ 79.95 % by mole and remaining aliphatic dihydroxy alcohol composition are formed,
The Co-b value of described fire-retardant master batch is-5 ~ 20, Co-L value is more than 50,
[changing 3]
5. fire-retardant master batch according to claim 4, wherein, the copolymerization ratio forming the Diethylene Glycol composition of described flame-retardant polyester resin is less than 30 % by mole.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-066755 | 2012-03-23 | ||
| JP2012066755 | 2012-03-23 | ||
| PCT/JP2013/054686 WO2013140947A1 (en) | 2012-03-23 | 2013-02-25 | Method for producing flame-retardant polyester, and flame-retardant master batch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104245789A true CN104245789A (en) | 2014-12-24 |
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|---|---|---|---|
| CN201380016178.9A Pending CN104245789A (en) | 2012-03-23 | 2013-02-25 | Method for producing flame-retardant polyester, and flame-retardant master batch |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2013140947A1 (en) |
| KR (1) | KR20140147804A (en) |
| CN (1) | CN104245789A (en) |
| TW (1) | TWI598376B (en) |
| WO (1) | WO2013140947A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785632A (en) * | 2022-11-30 | 2023-03-14 | 美瑞新材料股份有限公司 | High-fluidity high-toughness PLA/PBS (polylactic acid/poly (butylene succinate)) blend alloy material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102360899B1 (en) * | 2015-09-30 | 2022-02-08 | 코오롱인더스트리 주식회사 | Flame retardant polyester film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05178975A (en) * | 1991-12-28 | 1993-07-20 | Toyobo Co Ltd | Production of fire-resistant polyester |
| CN1890298A (en) * | 2003-12-09 | 2007-01-03 | 东洋纺织株式会社 | Thermoplastic resin composition for masterbatch, process for producing molding material comprising the same, thermoplastic resin composition obtained with the same, and process for producing the compo |
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| JP2551663B2 (en) * | 1989-09-11 | 1996-11-06 | 積水化学工業株式会社 | Method for producing aliphatic polyester |
| JP2000212266A (en) * | 1999-01-26 | 2000-08-02 | Nippon Ester Co Ltd | Preparation of flame-retardant polyester |
| JP4006629B2 (en) * | 2002-05-14 | 2007-11-14 | 東洋紡績株式会社 | Method for producing flame resistant polyester |
| JP2004002515A (en) * | 2002-05-31 | 2004-01-08 | Mitsubishi Chemicals Corp | Polyester resin, biaxially oriented film and insulating film for capacitor composed thereof |
| JP3934133B2 (en) * | 2003-12-09 | 2007-06-20 | 東洋紡績株式会社 | Thermoplastic resin composition for masterbatch, method for producing molding material thereof, thermoplastic resin composition using them, and method for producing the same |
| JP2006169358A (en) * | 2004-12-15 | 2006-06-29 | Nippon Ester Co Ltd | Flame-retardant polyester for fiber and method for producing the same |
| JP2007145727A (en) * | 2005-11-24 | 2007-06-14 | Sanko Kk | New organophosphorus compound and method for producing the same and polytrimethylene terephthalate |
| JP2008179714A (en) * | 2007-01-25 | 2008-08-07 | Teijin Fibers Ltd | Flame-retardant copolyester composition and flame-retardant polyester fiber |
| JP2010241974A (en) * | 2009-04-07 | 2010-10-28 | Teijin Fibers Ltd | Method for producing polyester |
| JP2011099004A (en) * | 2009-11-04 | 2011-05-19 | Teijin Dupont Films Japan Ltd | Polyester film for touch panel |
| JP2011231178A (en) * | 2010-04-26 | 2011-11-17 | Nippon Ester Co Ltd | Polyester elastomer resin composition |
| JP2012111812A (en) * | 2010-11-22 | 2012-06-14 | Toyobo Co Ltd | Polyester elastomer |
| JP2013018942A (en) * | 2011-07-14 | 2013-01-31 | Unitika Ltd | Flame-retardant polyester resin |
-
2013
- 2013-02-25 WO PCT/JP2013/054686 patent/WO2013140947A1/en active Application Filing
- 2013-02-25 CN CN201380016178.9A patent/CN104245789A/en active Pending
- 2013-02-25 JP JP2013548668A patent/JPWO2013140947A1/en active Pending
- 2013-02-25 KR KR1020147015718A patent/KR20140147804A/en not_active Application Discontinuation
- 2013-03-19 TW TW102109683A patent/TWI598376B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05178975A (en) * | 1991-12-28 | 1993-07-20 | Toyobo Co Ltd | Production of fire-resistant polyester |
| CN1890298A (en) * | 2003-12-09 | 2007-01-03 | 东洋纺织株式会社 | Thermoplastic resin composition for masterbatch, process for producing molding material comprising the same, thermoplastic resin composition obtained with the same, and process for producing the compo |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785632A (en) * | 2022-11-30 | 2023-03-14 | 美瑞新材料股份有限公司 | High-fluidity high-toughness PLA/PBS (polylactic acid/poly (butylene succinate)) blend alloy material and preparation method thereof |
| CN115785632B (en) * | 2022-11-30 | 2024-01-16 | 美瑞新材料股份有限公司 | High-fluidity high-toughness PLA/PBS (polylactic acid/Poly Butylene succinate) blending alloy material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI598376B (en) | 2017-09-11 |
| TW201343712A (en) | 2013-11-01 |
| JPWO2013140947A1 (en) | 2015-08-03 |
| KR20140147804A (en) | 2014-12-30 |
| WO2013140947A1 (en) | 2013-09-26 |
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Application publication date: 20141224 |