CN104558567A - A preparing method of halogen-free flame-retardant PBT copolyester - Google Patents
A preparing method of halogen-free flame-retardant PBT copolyester Download PDFInfo
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Abstract
A preparing method of halogen-free flame-retardant PBT copolyester is disclosed. Terephthalic acid and 1,4-butylene glycol are adopted as basic monomers. A halogen-free phosphorous compound is selected as a copolymerization flame retardant. The PBT copolyester is prepared by esterification, pre-polycondensation and final-polycondensation. The limiting oxygen index of the PBT copolyester can reach 29, the intrinsic viscosity is higher than 0.8 dL/g, and the PBT copolyester has good flame-retardant effects. During combustion, the PBT copolyester is free of generation of toxic compounds and is safe and environmental friendly to use. The flame retardant is introduced into PBT macromolecule chains in a flame retardant monomer manner to form the random or blocked flame-retardant copolyester, so that the PBT copolyester is durable in flame retardant performance, small in using amount of the flame retardant and uniform in dispersion, effectively retards flames and reduces the cost on the premise of ensuring mechanical performance of PBT, and is free of generation of side products after a plurality of times of processing.
Description
Technical field
The present invention relates to a kind of preparation method of PBT copolyesters, specifically relate to a kind of preparation method of fire retardant PBT with no halogen copolyesters, belong to PBT copolyesters technical field of modification.
Background technology
PBT(polybutylene terephthalate) be the thermoplastic polyester of hemicrystalline, there is high heat resistance, toughness, resistance to fatigue, the advantage such as self-lubricating, low-friction coefficient, be widely used in the fields such as automobile, electrical equipment, electronics, film, fiber, optical cable.But the large shortcoming of PBT mono-is than being easier to burning, limiting oxygen index(LOI) is about 20, and this characteristic makes PBT before the application of various fields, especially engineering materials field, needs to carry out fire-retardant finish to it.
Fire retardant and PBT base-material blending extrusion mainly obtain by the method flame-retardant modified to PBT at present, but there is following shortcoming in this method: first, due to fire retardant and PBT base-material be through blended after extrude obtained, fire retardant usually can be made to disperse uneven, flame retardant properties skewness, the usual addition that need increase fire retardant just can reach required flame retardant effect to 20 ~ 30% of total amount, but too much fire retardant is added into the mechanical properties decrease that PBT makes its material; Secondly, fire retardant disperse inequality in PBT, and can process and follow-up deposit in process, fire retardant is diffused to the surface, and formation " frosting " phenomenon, affects flame retardant effect equally; Again, according to inorganic combustion inhibitor, melt filtration degradation can be caused, affect post-treatment, as the making of fiber sprinning, masking and thin appliance element; Finally, if fire retardant and PBT base-material are through the blended processing of secondary, then side reaction inevitably occurs, as DeR, thus cause molecular weight and molecular weight, by product produces, and material property is influenced.
Meanwhile, carrying out another flame-retardant modified very important problem by fire retardant to PBT is whether adopted fire retardant can produce toxic compounds.What extensively adopt at present is halogen containing flame-retardant, as decabromodiphenyl oxide, decabromodiphenyl ethane, brominated epoxy resin, brominated Polystyrene etc., it can produce toxic compounds when burning, not only human body is damaged, also can cause corrosion to metal components and parts, the theory that environmental protection is more and more focused in this and global range every profession and trade field is disagreed.
Summary of the invention
The object of this invention is to provide a kind of good flame retardation effect solved the problems of the technologies described above, use environmental protection, human body is not damaged or metal components and parts are caused the preparation method of a kind of fire retardant PBT with no halogen copolyesters of corrosion.
Object of the present invention is realized by following technical proposals: a kind of preparation method of fire retardant PBT with no halogen copolyesters, comprises the steps:
Step one, by carboxylic for Halogen fire retardant and alcohol, esterification under 150 DEG C ~ 250 DEG C conditions obtains fire retardant carboxylate;
Step 2, by terephthalic acid, 1,4-butyleneglycol, the fire retardant carboxylate obtained become raw material slurry with catalyst mix, and 200 DEG C ~ 250 DEG C, carry out esterification 40min ~ 280min under absolute pressure 10kPa ~ 101kPa condition after obtain the mixture of mutual-phenenyl two acid bromide two alcohol ester, fire retardant carboxylate and catalyzer;
Step 3, by the mixture of step 2 product 220 DEG C ~ 250 DEG C, react 20min ~ 240min under 1kPa ~ 60kPa pressure condition, obtain the mixture of PBT performed polymer, fire retardant carboxylate and catalyzer;
Step 4, by the mixture of step 3 product 220 DEG C ~ 260 DEG C, under 10Pa ~ 500Pa condition polycondensation obtain fire retardant PBT with no halogen copolyesters.
Further, described fire retardant is organic phosphorus compound, and its structural formula is in the present invention:
Wherein, described R
1comprise alkyl, phenyl or naphthyl; Described R
2for
, wherein, n gets 1 ~ 4 random natural number.
The present invention further, esterification yield > 85 ﹪ of the fire retardant carboxylate described in step one, described alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, 1, ammediol or 1,4-butyleneglycol, described fire retardant is 1:1 ~ 1:20 with the ratio of the molar weight of described alcohol, and, the reactant added in step one also comprises esterifying catalyst, described esterifying catalyst comprises zinc acetate or tetrabutyl titanate, and its add-on counts 10ppm ~ 1000ppm with the quality of added zinc or titanium.
The present invention further, terephthalic acid described in step 2 and described 1, the ratio of 4-butyleneglycol molar weight is 1:1 ~ 2.5, the ratio of the molar weight of described terephthalic acid and described fire retardant carboxylate is 1:0.01 ~ 1, described catalyzer comprises tetrabutyl titanate, and the add-on of this catalyzer counts 10ppm ~ 500ppm with the quality of added titanium.
Utilization of the present invention and enforcement make its technique effect be mainly reflected in:
1. the present invention adopts the method for modification by copolymerization, with terephthalic acid and BDO for basic monomer, selects halogen-free phosphorus-containing compound to be copolymerization fire retardant, obtained fire retardant PBT with no halogen copolyesters, and its limiting oxygen index(LOI) can reach 29, has good flame retardant effect;
2. fire retardant PBT with no halogen copolyesters of the present invention is the phosphorous polymer not containing halogen, can not produce toxic substance, use safety environmental protection during its burning;
3. fire retardant of the present invention is introduced in PBT macromolecular chain with the form of flame-retardant monomer to form random or block inflaming retarding copolymer, its flame retardant properties is lasting, amount of flame-retardant agent is less, be uniformly dispersed, under the prerequisite ensureing PBT mechanical property, effectively fire-retardant and reduce costs, simultaneously because fire retardant existence form is stablized, repeatedly processing can not produce by product.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described, for embodiment be only to product of the present invention or method do generality illustrate, contribute to understanding the present invention better, but can't the scope of the invention be limited.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
The preparation method of fire retardant PBT with no halogen copolyesters of the present invention, details are as follows for its technical scheme:
First, by carboxylic for Halogen fire retardant and alcohol, esterification under 150 DEG C ~ 250 DEG C conditions obtains fire retardant carboxylate, and this fire retardant is for being specially organic phosphorus compound, and its structural formula is as follows:
Wherein, R
1comprise alkyl, phenyl or naphthyl, R
2for
, wherein, n gets 1 ~ 4 random natural number.Esterification yield > 85 ﹪ of obtained flame-retardant agent carboxylate, preferably more than 90%, described esterification yield to be defined as in fire retardant carboxylate acid number divided by saponification value; Described alcohol can be monohydroxy-alcohol or dibasic alcohol, includes but not limited to methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, 1,3-PD or BDO; The ratio of the molar weight of described fire retardant and described alcohol is between 1:1 ~ 1:20; Esterifying catalyst can also be comprised in the reactant that this step adds, described esterifying catalyst comprises zinc acetate or tetrabutyl titanate, its add-on counts 10ppm ~ 1000ppm with the quality of added zinc or titanium, certainly as is known to the person skilled in the art, also catalyzed reaction can be carried out under without esterifying catalyst condition, because above-mentioned fire retardant is halogen-free phosphorus-containing compound, fire retardant PBT with no halogen copolyesters of the present invention is made to be the phosphorous polymer not containing halogen, toxic substance can not be produced, use safety environmental protection during its burning.
Secondly, by terephthalic acid, 1,4-butyleneglycol, the fire retardant carboxylate obtained become raw material slurry with catalyst mix, and 200 DEG C ~ 250 DEG C, carry out esterification 40min ~ 280min under absolute pressure 10kPa ~ 101kPa condition after obtain the mixture of mutual-phenenyl two acid bromide two alcohol ester, fire retardant carboxylate and catalyzer.Now mainly terephthalic acid and 1,4-butyleneglycol carries out esterification and obtains mutual-phenenyl two acid bromide two alcohol ester, described terephthalic acid and described 1, the ratio of 4-butyleneglycol molar weight is 1:1 ~ 2.5, the ratio of the molar weight of described terephthalic acid and described fire retardant carboxylate is 1:0.01 ~ 1, described catalyzer comprises tetrabutyl titanate, and its add-on counts 10ppm ~ 500ppm with the quality of added titanium.
Again, by the mixture of mutual-phenenyl two acid bromide two alcohol ester, fire retardant carboxylate and catalyzer 220 DEG C ~ 250 DEG C, react 20min ~ 240min under 1kPa ~ 60kPa pressure condition, obtain the mixture of PBT performed polymer, fire retardant carboxylate and catalyzer.
Finally, by PBT performed polymer, the mixture of fire retardant carboxylate and catalyzer is at 220 DEG C ~ 260 DEG C, under 10Pa ~ 500Pa condition, polycondensation obtains fire retardant PBT with no halogen copolyesters of the present invention, therefore, the present invention is with terephthalic acid and 1, 4-butyleneglycol is basic monomer, be introduced in PBT macromolecular chain with the form of flame-retardant monomer and form random or block inflaming retarding copolymer, its flame retardant properties is lasting, amount of flame-retardant agent is less, be uniformly dispersed, under the prerequisite ensureing PBT mechanical property, effectively fire-retardant and reduce costs, simultaneously because fire retardant existence form is stablized, repeatedly processing can not produce by product, its limiting oxygen index(LOI) can reach 29, there is good flame retardant effect.
The inventive method can be carried out a stirring reactor discontinuous formula, and when reaction is carried out in a batch reactor, reactor is preferably stirring reactor, stirs paddle type and is preferably anchor formula oar.The top of reactor is connected with rectifying and dewatering tower, and when the esterification of needs negative pressure, rectifying tower top is connected with vacuum pump, is used for progressively setting up vacuum in esterification process.Also have a set of polycondensation vacuum system to be directly connected with reactor, for setting up preshrunk and polycondensation vacuum simultaneously.
When preparing fire retardant PBT with no halogen copolyesters, first above-mentioned raw materials is added in stirring reactor according to proportioning, adopt the air in nitrogen replacement esterifier, reaction can be carried out at normal pressure, also can carry out under negative pressure, along with the carrying out of reaction progressively sets up esterification vacuum, under 150 DEG C ~ 250 DEG C conditions, esterification obtains fire retardant carboxylate, obtaining product mixtures directly makes its environment at 200 DEG C ~ 250 DEG C, esterification is carried out under absolute pressure 10kPa ~ 101kPa condition, reaction 40min ~ 280min, obtain PBT carboxylate, the water that simultaneous reactions generates and Tetrahydrofuran are discharged from tower top, when the lime set of discharging is little, represent that esterification terminates.At this moment the valve be connected on dehydration tower is closed, open polycondensation vacuum system, open the valve that reactor is connected with polycondensation vacuum system gradually, 220 DEG C ~ 250 DEG C, under 1kPa ~ 60kPa pressure condition under carry out preshrunk reaction, reaction 20min ~ 240min obtains PBT performed polymer.By intensifying valve aperture or unlatching multistage vacuum pump, reactor carries out under higher vacuum, further 220 DEG C ~ 260 DEG C, 10Pa ~ 500Pa pressure condition carries out polycondensation, according to required molecular weight, or the limiting viscosity corresponding to molecular weight controls the reaction times, obtains required fire retardant PBT with no halogen copolyesters.
[embodiment 1]
A preparation method for fire retardant PBT with no halogen copolyesters, first: fire retardant 2-carboxyethyl phenyl Hypophosporous Acid, 50 30kg, mixes with 35kg ethylene glycol, be warmed up to 180 DEG C ~ 200 DEG C, esterification 240min, and the esterification yield of obtained flame-retardant agent carboxylate is 93.5%.Then: terephthalic acid 500kg, BDO 475kg, catalyzer tetrabutyl titanate 470g, join in stirred reactor together with above-mentioned fire retardant carboxylate, with the air in nitrogen replacement reactor, opens and stir and temperature reaction.
Temperature rises to 200 DEG C ~ 230 DEG C and carries out normal pressure esterification reaction, and esterification produces water and Tetrahydrofuran is discharged from tower top.Esterification 180min, tower top aquifer yield reduces to little, stops esterification, off-response device is connected with rectifying tower valve, open polycondensation vacuum pump, open the valve be connected with polycondensation vacuum pump gradually, the aperture of by-pass valve control, 240 DEG C, carry out preshrunk reaction under 1kPa ~ 60kPa pressure, reaction 60min, obtains PBT performed polymer, increases the aperture of valve further, at 245 DEG C, polycondensation 110min under 150Pa pressure, obtain the fire retardant PBT with no halogen copolyesters that limiting viscosity is 0.82dl/g.
Gained fire retardant PBT with no halogen copolyesters, recording its limiting oxygen index(LOI) according to national standard is 27.
[embodiment 2]
A preparation method for fire retardant PBT with no halogen copolyesters, first: fire retardant 2-carboxyethyl phenyl Hypophosporous Acid, 50 40kg, mixes with 46kg ethylene glycol, is warmed up to 180 DEG C ~ 200 DEG C esterification 4hr, and the esterification yield of obtained flame-retardant agent carboxylate is 92%.Then: terephthalic acid 500kg, BDO 475kg, catalyzer tetrabutyl titanate 470g, join in stirred reactor together with above-mentioned fire retardant carboxylate, with the air in nitrogen replacement reactor, opens and stir and temperature reaction.
Temperature rises to 200 DEG C ~ 230 DEG C and carries out normal pressure esterification reaction, and esterification produces water and Tetrahydrofuran is discharged from tower top.Esterification 190min, tower top aquifer yield reduces to little, stop esterification, off-response device is connected with rectifying tower valve, opens polycondensation vacuum pump, opens the valve be connected with polycondensation vacuum pump gradually, the aperture of by-pass valve control, 240 DEG C, carry out preshrunk reaction under 1kPa ~ 60kPa pressure, reaction 60min, obtains PBT performed polymer.The aperture of further increase valve, at 245 DEG C, polycondensation 120min under 150Pa pressure, obtains the fire retardant PBT with no halogen copolyesters that limiting viscosity is 0.83dl/g.
Gained fire retardant PBT with no halogen copolyesters, recording its limiting oxygen index(LOI) according to national standard is 29.
[embodiment 3]
A preparation method for fire retardant PBT with no halogen copolyesters, first: fire retardant 2-carboxyethyl methylphosphinate Hypophosporous Acid, 50 29kg, mixes with 46kg ethylene glycol, is warmed up to 150 DEG C ~ 200 DEG C esterification 3hr, and the esterification yield of obtained flame-retardant agent carboxylate is 93%.Then: terephthalic acid 500kg, BDO 475kg, catalyzer tetrabutyl titanate 470g, join in stirred reactor together with above-mentioned fire retardant carboxylate, with the air in nitrogen replacement reactor, opens and stir and temperature reaction.
Temperature rises to 200 DEG C ~ 230 DEG C and carries out normal pressure esterification reaction, and esterification produces water and Tetrahydrofuran is discharged from tower top.Esterification 190min, tower top aquifer yield reduces to little, stop esterification, off-response device is connected with rectifying tower valve, opens polycondensation vacuum pump, opens the valve be connected with polycondensation vacuum pump gradually, the aperture of by-pass valve control, 240 DEG C, carry out preshrunk reaction under 1kPa ~ 60kPa pressure, reaction 60min, obtains PBT performed polymer.The aperture of further increase valve, at 245 DEG C, polycondensation 120min under 150Pa pressure, obtains the fire retardant PBT with no halogen copolyesters that limiting viscosity is 0.83dl/g.
Gained fire retardant PBT with no halogen copolyesters, recording its limiting oxygen index(LOI) according to national standard is 28.
[embodiment 4]
A kind of preparation method of fire retardant PBT with no halogen copolyesters, first: fire retardant 2-carboxyethyl phenyl Hypophosporous Acid, 50 137kg/hr, mix with 160kg/hr ethylene glycol, join in fire retardant reaction kettle of the esterification, be warmed up to 180 DEG C ~ 200 DEG C esterifications, the residence time is 240min, and the esterification yield of obtained flame-retardant agent carboxylate reaches 93.5%, and above-mentioned fire retardant carboxylate enters into PBT reaction kettle of the esterification again.
2293 kg/hr terephthalic acids, 1380 kg/hr 1,4-butyleneglycol, 1.9kg/hr metatitanic acid acid, four butyl ester catalyzer, join in slurry tank, after being prepared into slurry mix, enter into PBT reaction kettle of the esterification, esterification is carried out at 240 DEG C, the pressure-controlling of esterification is at 45kPa, and the steam at esterifier top enters into dehydration tower, removes water and the Tetrahydrofuran of esterification generation from top, the BDO that bottom obtains turns back in esterifier.Material after esterification enters into finishing reaction still, carries out polycondensation, reaction pressure control 10kPa, and temperature controls at 245 DEG C, and the BDO that polycondensation removes out and by product recycle.Aftercondensated reactant out enters into whole batch condensation polymerization reactor and carries out further polycondensation, temperature of reaction controls at 250 DEG C, pressure-controlling is at 100Pa, whole batch condensation polymerization reactor material out enters into granulating equipment granulation and obtains required fire retardant PBT with no halogen copolyesters product, and recording limiting oxygen index(LOI) according to national standard is 27.
It should be noted that above-described embodiment is only used for explaining explanation, and should not be counted as the restriction to institute of the present invention content scope.Limit for fear of length, only describe comparatively typical implementation method in detail, should be fully recognized that the present invention can make related amendments for the innovative point and advantage not departing from its content purport for a person skilled in the art, and all this kind of amendments all should be included in that the present invention defines with context that is equivalent within.Must be recognized that in addition, be included in some implementation methods in context of the present invention, may be identified certain advantage without some other implementation method, but the shortage of this specific advantages does not should be understood to this implementation method certainty outside institute of the present invention content scope.
Claims (8)
1. the preparation method of fire retardant PBT with no halogen copolyesters, is characterized in that comprising the steps:
Step one, by carboxylic for Halogen fire retardant and alcohol, esterification under 150 DEG C ~ 250 DEG C conditions obtains fire retardant carboxylate;
Step 2, by terephthalic acid, 1,4-butyleneglycol, described fire retardant carboxylate become raw material slurry with catalyst mix, and at 200 DEG C ~ 250 DEG C, esterification 40min ~ 280min under absolute pressure 10kPa ~ 101kPa condition, obtain the mixture of mutual-phenenyl two acid bromide two alcohol ester, described fire retardant carboxylate and described catalyzer;
Step 3, by the mixture of step 2 product 220 DEG C ~ 250 DEG C, react 20min ~ 240min under 1kPa ~ 60kPa pressure condition, obtain the mixture of PBT performed polymer, described fire retardant carboxylate and described catalyzer;
Step 4, by the mixture of step 3 product 220 DEG C ~ 260 DEG C, under 10Pa ~ 500Pa condition polycondensation obtain fire retardant PBT with no halogen copolyesters.
2. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, is characterized in that: described fire retardant is organic phosphorus compound, and its structural formula is:
In formula, R
1for alkyl, phenyl or naphthyl; R
2for
, wherein, n gets 1 ~ 4 random natural number.
3. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, is characterized in that: esterification yield > 85 ﹪ of the fire retardant carboxylate in step one.
4. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, is characterized in that: alcohol described in step one comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, 1,3-PD or BDO.
5. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, is characterized in that: fire retardant described in step one is 1:1 ~ 1:20 with the ratio of the molar weight of described alcohol.
6. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, it is characterized in that: the reactant added in step one also comprises esterifying catalyst, described esterifying catalyst comprises zinc acetate or tetrabutyl titanate, and its add-on counts 10ppm ~ 1000ppm with the quality of added zinc or titanium.
7. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, it is characterized in that: terephthalic acid described in step 2 and described 1, the ratio of 4-butyleneglycol molar weight is 1:1 ~ 2.5, and the ratio of the molar weight of described terephthalic acid and described fire retardant carboxylate is 1:0.01 ~ 1.
8. the preparation method of fire retardant PBT with no halogen copolyesters according to claim 1, it is characterized in that: the catalyzer described in step 2 comprises tetrabutyl titanate, its add-on is counted as 10ppm ~ 500ppm with the quality of added titanium.
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Application publication date: 20150429 |