CN101275010A - Flame-proof reinforced Valox compound and preparation thereof - Google Patents

Abstract

The invention discloses a flame retardant intensified polybutylene terephthalate composite and a preparation method thereof; weight portions of the compositions for preparing the flame retardant intensified polybutylene terephthalate composite are: 100 portions of medium viscosity PBT resin, 15 to 30 portions of brominated flame retardants, 10 to 30 portions of composite mother particles, and 15 to 150 portions of fiber glass. The product of the invention has good stability of heat resistance and oxygen aging in the treatment process and good stability of heat resistance and oxygen aging in long-term use at high temperature, so light color and bright color products are difficult to change color during the processing period, and difficult to turn yellow or black under long-term use at high temperature, which can satisfy the application in long-term use at high temperature for electronic and electrical components and appearance parts and large power energy-saving light.

Description

Fire-retardant enhancing polybutylene terephthalate mixture and preparation method thereof

Technical field

The present invention relates to a kind of fire-retardant enhancing polybutylene terephthalate mixture and preparation method thereof, the environmental protection flame retardant that relates in particular to anti-xanthochromia, rapid shaping strengthens polybutylene terephthalate mixture and preparation method thereof.

Background technology

Polybutylene terephthalate is called for short PBT, is a kind of engineering plastics with general high-performance, particularly excellent electric performance; But because PBT belongs to crystalline material, heat-drawn wire own is low, and notch shock susceptibility is strong, poor dimensional stability, and easy firing, shaping cycle is long, difficult processing, thereby limited its use range.PBT is carried out extensive study on the modification both at home and abroad, mainly be the research of toughness reinforcing, enhancing, fire-retardant, blending and modifying and chemical chain extension for this reason.Most widely used is flame-retardant reinforced PBT, it is mainly used in electronic apparatus structural part and appearance component, in recent years, the raising of popularizing and requiring along with the electricity-saving lamp application, the application of PBT is extended on the electricity-saving lamp lamp socket, particularly seems more outstanding on powerful electricity-saving lamp and high-end operating device.

The producer of universal environmental protection of domestic production at present and non-environment-friendly flame-retardant reinforced PBT is more, but because the adding of fire retardant descends the course of processing heat oxygen aging resistance stability of PBT and the heat oxygen aging resistance stability of long term high temperature use significantly, make in the course of processing light color and the very easily variable color of bright look product, and very easily flavescence under the long term high temperature use, blackening.Can't satisfy electronic apparatus structural part and appearance component, high-power energy-saving lamp long term high temperature environment for use.In short supply along with the energy enhanced productivity, and shortening shaping cycle also is the serious problems that universal environmental protection and non-environment-friendly flame-retardant reinforced PBT face, and this has just proposed new, higher requirement to universal environmental protection and non-environment-friendly flame-retardant reinforced PBT.

The producer of the anti-xanthochromia of external production, environment-friendly flame-retardant reinforced PBT and rapid shaping, environment-friendly flame-retardant reinforced PBT is also more, and not only anti-xanthochromia is not separated out but also the producer of rapid shaping multi-functional environment-protection flame-retardant reinforced PBT and few but produce.

Summary of the invention

The purpose of this invention is to provide a kind of fire-retardant enhancing polybutylene terephthalate mixture and preparation method thereof, to overcome the above shortcoming of domestic current material.

Fire-retardant enhancing polybutylene terephthalate mixture provided by the present invention, its parts by weight consist of:

In 100 parts of sticking PBT resins, brominated flame retardant 15-30 part, composite master batch 10-30 part, glass fibre 15-150 part;

The solution solvent viscosity ratio of sticking PBT resin is 0.85-1.2 in said;

The definition of term " solution solvent viscosity ratio " is the viscosity and the synthermal ratio of the viscosity of solution down of neat solvent;

Said brominated flame retardant is selected from bromination phenyl indane, (its molecular formula is C11H8O6Br to phosphoric acid ester to cage shape (2,4,6-tribromo phenyl) two (1-oxo-4-methylene-2,6,7-three Oxy-1s-phospha dicyclo (2.2.2) octyl)₃P), two (2,4,6-tribromo phenyl) (its molecular formula is C11H9NO5Br to phosphoric acid ester to cage shape (1-oxo-4-methylene-2,6,7-three Oxy-1s-phospha dicyclo (2.2.2) octyl)₃P), brominated Spirocyclic 3, two (the pentabromo-phenoxy groups)-2,4,8 of 9-, 10-four oxos-3, (its molecular formula is C 17H8O8Br to 9-hosphospiro [5.5]-3,9 dioxy undecane₁₀P₂), dibromo neopentyl alcohol, brominated epoxy resin oligopolymer (Dead Sea Bromine Group F-2000 series, F-3000 series), 2,4,6-allyl tribromide acid phenenyl ester, polyacrylic acid pentabromo-benzyl ester, condensed bromoacenaphthylene oligopolymer, TDE, two (2, the 3-dibromopropyl) fumarate, phenoxy group tetrabromobisphenol a polycarbonate oligopolymer, dibromo phenyl glycidyl ester, vinylformic acid pentabromo-benzyl ester, tribromo phenyl maleimide, Dowspray 9 oligopolymer are (as DSB_rThe CN-323 of G company, CN-1427 etc.), bromophthalic acid ester, ten tetrabromos, two phenoxy groups, 1, two (2,4, the 6-tribromophenoxy) ethane of 2-, tetrabromophthalic anhydride, tetrabromo-phthalate, DBS oligopolymer are (as DSB_rThe Homopolymer ofDibromostyrene of G company, Homopolymer ofDibromo and tribromo styrene etc.), two (3-bromo-2,2-dibromo methyl-propyl) sulfite, ten dibromos, two phenoxy group benzene or Dechlorane plus25 or the like;

The parts by weight of said composite master batch consist of: 100 parts of low glutinous PBT resins, ionic elastomerics 10-30 part, auxiliary mineral powder fire retardant 5-20 part, composite assistant 1-10 part;

The solution solvent viscosity ratio of low glutinous PBT resin is 0.72-0.86;

The ionic elastomerics is selected from the methacrylic acid group by Zinc ion 5-30% neutral ethylene/methacrylic acid, introduces the third comonomer in polymerization process its rigidity is descended, and snappiness increases, as Surlyn9320.Another kind is that the methacrylic acid group is by Zinc ion 20-80% neutral ethylene/methacrylic acid, introducing the third comonomer in polymerization process increases its cold resistance, as Surlyn9020, the third comonomer is an acrylate, degree of neutralization is 1-30%, when in it and degree when being 5-15%, be optimised, demonstrate its optimized over-all properties.Adopt the commercially available prod, the trade mark of producing as DUPONT company is the product of Surlyn9320 or Surlyn9020.

Said auxiliary mineral powder fire retardant is selected from zeolite, three cobalt oxides, titanium dioxide, three oxidations, two berylliums, zinc selenate, zinc borate, zinc phosphate, the o-Hydroxytoluene formaldehyde epoxy resin, ferric oxide, zinc oxide, the FRX-1071 inorganic composite flame retardants that ALBEMARLE company produces, wollastonite, zirconium silicate, talcum powder, magnesiumcarbonate, silicon-dioxide, magnesia crystal whisker, the nickel oxide whisker, alumina whisker, silicon carbide whisker, the GaAs whisker, mica, magnesium hydroxide, potassium felspar sand, silicon-dioxide, in magnesiumcarbonate or the talcum powder more than one;

Said composite assistant is mainly the mixture of nucleator, thermo oxidative aging agent and auxiliary thermo oxidative aging agent, in the gross weight of composite assistant:

The parts by weight of nucleator are 20～40 parts, and the parts by weight of thermo oxidative aging agent are 50～40 parts, and the parts by weight of auxiliary thermo oxidative aging agent are 30～20 parts.

Said nucleator is selected from long-chain linear saturated carboxylic acid sodium salt, long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide; Said long-chain linear saturated carboxylic acid sodium salt, long carbochain carboxylic acid calcium salt can adopt the commercially available prod, as the trade(brand)name MJ1032 of Clariant company production, the product of MJ1030;

The thermo oxidative aging agent is selected from Hinered phenols or amine;

Hinered phenols is as A0-30, A0-40, A0-50, A0-60, triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, (2,4,6-trioxy--1,3,5-triazines-1,3,5 (2H, 4H, 6H)-three base) trivinyl three (3-(3, the 5-di-tert-butyl-hydroxy phenyl) acrylate), 2,2 '-(3-(3 for thiobis, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate), 3,5-two (1, the 1-dimethyl ethyl)-(3-(3 for 4-hydroxy phenylpropionic acid 2-, 5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyl)-and the 1-oxopropyl) hydrazides, N, N '-1,6-dihexyl two (3,5-two (1,1-dimethyl ethyl-4-hydroxybenzene propionyl);

Amine is as N, and N-is two-(3-(3, the 5-di-t-butyl) propionyl) hexanediamine, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene etc.);

Auxiliary thermo oxidative aging agent is selected from the solid aromatic phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl-4,4 ' xenyl) biphosphonate, distearyl pentaerythritol diphosphite, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, (18) ester on the thio-2 acid, Tyox B or the like.

The preparation method of fire-retardant enhancing polybutylene terephthalate mixture of the present invention comprises the steps:

(1) preparation of composite master batch:

In order to give full play to the elastomeric effect of various auxiliary agents and ionic, to assist mineral powder fire retardant to carry out admixture activation with surface treatment agent earlier in 102～107 ℃ high mixer handled 10～30 minutes, surface treatment agent is the material of high molecular organic silicone oil, phosphate coupling agent, aluminate coupling agent, titanate coupling agent, silane coupling agent, Resins, epoxy treatment agent, glycidyl methacrylate or commodity SFR-100 by name, and the weight consumption of surface treatment agent is 0.5～5% of auxiliary mineral powder fire retardant;

Proportionally low-viscosity PBT resin, ionic elastomerics and composite assistant are mixed, the auxiliary mineral powder fire retardant after surface treatment is sent into twin screw extruder plasticizing, mixing then, obtains composite master batch;

(2) will in sticking PBT resin mixes with the composite master batch of step (1), send into the twin screw extruder plasticizing, subsequently resistance agent of environmental protection bromination and glass are fed twin screw extruder by side feeding gauger, mixing, the acquisition product.

The length-to-diameter ratio of twin screw extruder is at least 28～40, has three cover drawing-in devices at least;

Among the preparation method of composite master batch of the present invention, the main-machine screw rotating speed is preferably between 250-500 rev/min between 200-550 rev/min, and each section extruder temperature is controlled between 160-260 ℃, preferably is controlled between 180-250 ℃.

Among the preparation method of step (2), the main-machine screw rotating speed is preferably between 250-450 rev/min between 200-500 rev/min, and each section extruder temperature is controlled between 215-295 ℃, preferably is controlled between 225-270 ℃.

Product of the present invention, the heat oxygen aging resistance good stability that course of processing heat oxygen aging resistance stability and long term high temperature use, make in the course of processing light color and bright look product not easy to change, and inhibited from yellowing, blackening under long term high temperature uses can be satisfied electronic apparatus structural part and appearance component, high-power energy-saving lamp long term high temperature environment for use.

Embodiment

Embodiment 1

(1) preparation of composite master batch:

Earlier be that wollastonite, zinc oxide, silicon carbide whisker carry out admixture activation with 0.6 kilogram of surface treatment agent in (parts by weight) ratio of 200: 300: 1 and handled 20 minutes in 105 ℃ high mixer with 100.2 kilograms of auxiliary mineral powder fire retardants, surface treatment agent is 0.3 kilogram of silane coupling agent, 0.1 kilogram of high molecular organic silicone oil and 0.2 kilogram of Resins, epoxy mixed solution;

With 100 kilograms of viscositys is that 0.72 low glutinous PBT resin, 25 kilograms of ionic elastomericss and 2 kilograms of composite assistants mix, auxiliary mineral powder fire retardant after 7 kilograms of surface treatments is sent into twin screw extruder plasticizing, mixing then, obtains composite master batch;

The ionic elastomerics is that acrylic acid groups is by Zinc ion part neutral ethylene/methacrylic acid, contain the third acrylate co-monomers in the multipolymer, is degree of neutralization? 1-30%, the trade mark that adopts Dupont company to produce is Surlyn 9320 products;

Composite assistant adopt triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester and long-chain linear saturated carboxylic acid sodium salt be by the mixture of 2: 1: 2 parts by weight;

(2) with 100 kilograms of viscositys be 1.05 PBT resin and 25 kilograms; the composite master batch of step (1) mixes, and sends into the twin screw extruder plasticizing, subsequently 25 kilograms of polyacrylic acid pentabromo-benzyl esters and 65 kilograms of glasses is fed twin screw extruder by side feeding gauger; mixing, obtain product.

The length-to-diameter ratio of twin screw extruder is 32, has three cover drawing-in devices;

The main-machine screw rotating speed is at 400 rev/mins, and each section extruder temperature is controlled at 210-250 ℃.

Among the preparation method of step (2), the main-machine screw rotating speed is at 350 rev/mins, and each section extruder temperature is controlled at 210-270 ℃.

Detected result is as follows:

Embodiment 2

(1) preparation of composite master batch:

Earlier be that zeolite, zinc borate, magnesia crystal whisker carry out admixture activation with 1.5 kilograms of surface treatment agents in (parts by weight) ratio of 200: 300: 1 and handled 20 minutes in 105 ℃ high mixer with 100.2 kilograms of auxiliary mineral powder fire retardants, surface treatment agent is 0.6 kilogram of silane coupling agent, 0.3 kilogram of high molecular organic silicone oil and 0.6 kilogram of Resins, epoxy mixed solution;

With 100 kilograms of viscositys is that 0.72 low glutinous PBT resin, 15 kilograms of ionic elastomericss and 6 kilograms of composite assistants mix, auxiliary mineral powder fire retardant after 15 kilograms of surface treatments is sent into twin screw extruder plasticizing, mixing then, obtains composite master batch;

The ionic elastomerics is that acrylic acid groups is by Zinc ion part neutral ethylene/methacrylic acid, contain the third acrylate co-monomers in the multipolymer, is degree of neutralization? 1-30%, the trade mark that adopts Dupont company to produce is Surlyn 9020 products;

Composite assistant adopts 3,5-two (1, the 1-dimethyl ethyl)-(3-(3 for 4-hydroxy phenylpropionic acid 2-, 5-two (1, the 1-dimethyl ethyl)-the 4-hydroxy phenyl)-the 1-oxopropyl) hydrazides, four (2,4-di-tert-butyl-phenyl-4,4 ' xenyl) biphosphonate and long-chain linear saturated carboxylic acid sodium salt are by the mixture of 2: 1: 2 parts by weight;

(2) with 100 kilograms of viscositys be 1.05 PBT resin and 15 kilograms; the composite master batch of step (1) mixes, and sends into the twin screw extruder plasticizing, subsequently 20 kilograms of brominated epoxy resin F2400 and 65 kilograms of glasses is fed twin screw extruder by side feeding gauger; mixing, obtain product.

The length-to-diameter ratio of twin screw extruder is 32, has three cover drawing-in devices;

The main-machine screw rotating speed changes a part clock 400, and each section extruder temperature is controlled at 210-250 ℃.

Among the preparation method of step (2), the main-machine screw rotating speed is at 350 rev/mins, and each section extruder temperature is controlled at 210-280 ℃.

Detected result is as follows:

Claims (10)

1. fire-retardant enhancing polybutylene terephthalate mixture is characterized in that parts by weight consist of: in 100 parts of sticking PBT resins, brominated flame retardant 15-30 part, composite master batch 10-30 part, glass fibre 15-150 part;

The solution solvent viscosity ratio of sticking PBT resin is 0.85-1.2 in said;

The parts by weight of said composite master batch consist of: 100 parts of low-viscosity PBT resins, ionic elastomerics 10-30 part, auxiliary mineral powder fire retardant 5-20 part, composite assistant 3-10 part;

The solution solvent viscosity ratio of low-viscosity PBT resin is 0.72-0.86;

The ionic elastomerics is selected from the methacrylic acid group by Zinc ion 1-30% neutral ethylene/methacrylic acid, introduces the third acrylate co-monomers in polymerization process its rigidity is descended, and snappiness increases.Another kind be the methacrylic acid group by Zinc ion 1-30% neutral ethylene/methacrylic acid, this product has good cold resistance.

Said composite assistant is mainly the mixture of nucleator, thermo oxidative aging agent and auxiliary thermo oxidative aging agent.

2. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1 is characterized in that in the ionic elastomerics, the third comonomer is an acrylate, and degree of neutralization is 1-30%.

3. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1, it is characterized in that, said brominated flame retardant is selected from bromination phenyl indane, cage shape (2,4,6-tribromo phenyl) two (1-oxos-4-methylene-2,6,7-three Oxy-1s-phospha dicyclo (2,2,2) phosphoric acid ester octyl), cage shape (1-oxo-4-methylene-2,6,7-three Oxy-1s-phospha dicyclo (2,2,2) octyl) two (2,4,6-tribromo phenyl) phosphoric acid ester, the dibromo neopentyl alcohol, the brominated epoxy resin oligopolymer, 2,4,6-allyl tribromide acid phenenyl ester, polyacrylic acid pentabromo-benzyl ester, the condensed bromoacenaphthylene oligopolymer, TDE, two (2, the 3-dibromopropyl) fumarate, phenoxy group tetrabromobisphenol a polycarbonate oligopolymer, the dibromo phenyl glycidyl ester, vinylformic acid pentabromo-benzyl ester, tribromo phenyl maleimide, the Dowspray 9 oligopolymer, the bromophthalic acid ester, ten tetrabromos, two phenoxy groups, 1,2-two (2,4, the 6-tribromophenoxy) ethane, tetrabromophthalic anhydride, tetrabromo-phthalate, the DBS oligopolymer, two (3-bromo-2,2-dibromo methyl-propyl) sulfites or ten dibromos, two phenoxy group benzene or Dechlorane plus25.

4. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1, it is characterized in that said auxiliary mineral powder fire retardant is selected from zeolite, three cobalt oxides, titanium dioxide, three oxidations, two berylliums, zinc selenate, zinc borate, zinc phosphate, the o-Hydroxytoluene formaldehyde epoxy resin, ferric oxide, zinc oxide, FRX-1071, wollastonite, zirconium silicate, talcum powder, magnesiumcarbonate, silicon-dioxide, magnesia crystal whisker, the nickel oxide whisker, alumina whisker, silicon carbide whisker, the GaAs whisker, mica, magnesium hydroxide, potassium felspar sand, silicon-dioxide, in magnesiumcarbonate or the talcum powder more than one.

5. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1, it is characterized in that, said composite assistant is mainly the mixture of nucleator, thermo oxidative aging agent and auxiliary thermo oxidative aging agent, in the gross weight umber of composite assistant:

The parts by weight of nucleator are 20～40 parts, and the parts by weight of thermo oxidative aging agent are 50～40 parts, and the parts by weight of auxiliary thermo oxidative aging agent are 30～20 parts.

6. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1, it is characterized in that, said nucleator is selected from long-chain linear saturated carboxylic acid sodium salt, long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide, and the thermo oxidative aging agent is selected from Hinered phenols or amine.

7. fire-retardant enhancing polybutylene terephthalate mixture according to claim 6 is characterized in that Hinered phenols is selected from A0-30, A0-40, A0-50, A0-60, triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, and the β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) trivinyl three (3-(3, the 5-di-tert-butyl-hydroxy phenyl) acrylate), 2,2 '-(3-(3 for thiobis, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate), 3,5-two (1, the 1-dimethyl ethyl)-(3-(3 for 4-hydroxy phenylpropionic acid 2-, 5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyl)-and the 1-oxopropyl) hydrazides, N, N '-1,6-dihexyl two (3,5-two (1,1-dimethyl ethyl-4-hydroxybenzene propionyl);

Amine is selected from N, and N-pair-(3-(3, the 5-di-t-butyl) propionyl) hexanediamine, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.

8. fire-retardant enhancing polybutylene terephthalate mixture according to claim 1, it is characterized in that auxiliary thermo oxidative aging agent is selected from the solid aromatic phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl-4,4 ' xenyl) biphosphonate, distearyl pentaerythritol diphosphite, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, thio-2 acid (18) ester or Tyox B.

9. the preparation method of each described fire-retardant enhancing polybutylene terephthalate mixture of claim 1～8 comprises the steps:

(1) preparation of composite master batch:

In order to give full play to the elastomeric effect of various auxiliary agents and ionic, to assist mineral powder fire retardant to carry out admixture activation with surface treatment agent earlier in 102～107 ℃ high mixer and handle 10～30 minutes, surface treatment agent is the material of high molecular organic silicone oil, phosphate coupling agent, aluminate coupling agent, titanate coupling agent, silane coupling agent, Resins, epoxy treatment agent, glycidyl methacrylate or commodity SFR-100 by name;

Proportionally low-viscosity PBT resin, ionic elastomerics and composite assistant are mixed, the auxiliary mineral powder fire retardant after surface treatment is sent into twin screw extruder plasticizing, mixing then, obtains composite master batch;

(2) will in sticking PBT resin mixes with the composite master batch of step (1), send into the twin screw extruder plasticizing, subsequently resistance agent of environmental protection bromination and glass are fed twin screw extruder by side feeding gauger, mixing, the acquisition product.

10. method according to claim 9, it is characterized in that, the weight consumption of surface treatment agent is 0.5～10% of auxiliary mineral powder fire retardant, the length-to-diameter ratio of twin screw extruder is at least 28～40, at least have three cover drawing-in devices, among the preparation method of composite master batch, the main-machine screw rotating speed is between 200-550 rev/min, each section extruder temperature is controlled between 160-260 ℃, among the preparation method of step (2), the main-machine screw rotating speed is between 200-500 rev/min, and each section extruder temperature is controlled between 215-295 ℃.