CN102532830A - Halogen-free phosphorus-free flame-retarding toughening master batch special for PBT (polybutylene terephthalate) and preparation method thereof - Google Patents
Halogen-free phosphorus-free flame-retarding toughening master batch special for PBT (polybutylene terephthalate) and preparation method thereof Download PDFInfo
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- CN102532830A CN102532830A CN2012100319766A CN201210031976A CN102532830A CN 102532830 A CN102532830 A CN 102532830A CN 2012100319766 A CN2012100319766 A CN 2012100319766A CN 201210031976 A CN201210031976 A CN 201210031976A CN 102532830 A CN102532830 A CN 102532830A
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Abstract
The invention provides a halogen-free phosphorus-free flame-retarding toughening master batch special for PBT (polybutylene terephthalate) and a preparation method thereof. The master batch is characterized in that the raw material formulation comprises the following components in percentage by weight: 20-60% of PBT resin, 70-35% of halogen-free phosphorus-free flame retardant, 5-10% of toughening agent, 0.2-0.6% of antioxidant, 1-3% of lubricating and dispersing agent and 0.2-1% of coupling agent. In the preparation method, PBT is used as a carrier, and PDPTP is used as the halogen-free phosphorus-free flame retardant; after surface treatment is carried out, the toughening agent, the dispersing agent and the antioxidant are added, and extrusion and granulation are carried out through two screws so as to prepare the halogen-free phosphorus-free flame-retarding toughening master batch special for PBT. According to the invention, the environment-friendly index of the prepared master batch meets the requirements of European Union RoHS (Restricted of Hazardous Substances), IEC (International Electrotechnical Commission) halogenation-free and Reach laws; and the prepared master batch can be used for modification of PBT, thus the flame-retarding grade of PBT reaches American UL 940.8mm V-0 grade, the CTI (comparative cracking index) value reaches more than 425V, the glowing filament experiment temperature reaches 750 DEG C but firing is not generated, and match color is not influenced.
Description
Technical field
The present invention relates to the polymer modification field, be specifically related to special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of a kind of PBT and preparation method thereof.This master batch can be used for the halogen-free flame-proof toughening enhancing modified of PBT, also can be used for PET, PTT etc., and flame retardant resistance after its modification and each side mechanical property are ideal.PBT is material modified for the halogen-free flame-proof toughening enhanced, is widely used in industry and fields such as electric, IT, aerospace, automobile, household electrical appliance, medical treatment and sports apparatus.
Background technology
All the time; The fire retardant that is used for modifying plastics is main with bromo-antimony compound system; This system good flame retardation effect, addition are low, little to the mechanical property influence of material; But it can produce toxic substances such as hydrogen halide, dioxin in the process of combustion decomposition, all can cause greatly people's health and environment and endanger.To the influence of the electrical property of material very big (as CTI value below 175V), and in the course of processing, be prone to bloom, be prone to block up venting port, mould is had corrosive nature.Along with the whole world particularly developed country such as America and Europe environmental protection and public safety are required progressively to improve; A lot of in the world well-known electronic enterprises, IT industry (like Dell, Sony, Samsung, LG, Sony-Ericson, association, Benq etc.) all require non-halogen to the fire-retardant component materials in its product; And all proposed concrete standard, last implementation period was limited to for the end of the year 2009.International Power committee (IEC) has also put into effect non-halogen standard, requires in the material Cl distinguish must not above 900PPm with Br, and the two content must not amount to above 1500PPm.So fire retardant material is non-halogen extremely urgent.But several kinds of common halogen-free flame retardantss all have all drawbacks, and range of application is very limited.Like the conventional red phosphorus fire retardant, good flame retardation effect, little to the material mechanical performance influence, but can only do black or garnet product, smell is big, is prone to separate out, and when injection moulding, is prone to dieseling.The oxyhydroxide fire retardant will reach flame retardant effect, needs heavy addition, and is very big, also inadvisable to the mechanical property influence of material.Also useful phosphorus-nitrogen combustion inhibitor is joined mutually, but flame retardant effect is very poor, does not reach the UL940.8mm V-0 level of electric industry universal demand.
The non-halogen flame-retarded technology of materials such as nylon, PP, ABS is relatively easy at present, and the fire retardant of more existing high performance-price ratios occurs in market, but the non-halogen flame-retardant modified technology of PBT and product are world-famous puzzles always.At present, the fire retardant OP1240 that German Clariant company produces, it is best to be used for the flame-retardant modified over-all properties of PBT, but this product can only rely on import; Cost an arm and a leg, inadequate supply, and also addition is big; Because be pulvis, processing difficulties requires harsh to complete processing and forcing machine again.Product of the present invention (being the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT) synthesizes through hundreds of and application test just develops; This product is used for the PBT good flame retardation effect, and is little to the mechanical property influence of material, good electrical property; Do not influence color matching; The environmental protection aspect meets ROHS of European Union and Reach statutory standard, satisfy the non-halogen standard of IEC fully, and cost can reduce greatly.Therefore the invention of the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of this PBT; Be a kind of new breakthrough to the flame-retardant modified technology of PBT material, the technical progress and the industrial upgrading of PBT Application Areas such as electric, the IT of force urges, aerospace, automobile, household electrical appliance, medical treatment and sports apparatus and industry greatly.Because this invention can realize fire-retardant non-halogen fully of PBT, meets up-to-date environmental requirement, can greatly promote energy-saving and emission-reduction, also is a quantum jump aspect environmental protection.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists; Provide that a kind of environmental protection index can satisfy the RoHS of European Union, IEC is non-halogen and the Reach laws and regulations requirement; Can make the modified PBT Flame Retardancy reach U.S. UL940.8mm V-0 level; Creepage trace index (CTI) value reaches more than the 425V, glowing filament (GWIT) experimental temperature reach 750 ℃ not on fire, and do not influence the halogen-free phosphorus-free inflaming retarding plasticizing mother particle of color matching fully.
Another object of the present invention provides the preparation method of the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of above-mentioned PBT.
For achieving the above object, the technical scheme that the present invention adopts is:
1. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of a PBT, composition of raw materials is (percentage ratio by weight):
(1) PBT resin---20～60%;
(2) halogen-free phosphorus-free inflaming retarding agent---70～35%;
(3) toughner---5～10%;
(4) oxidation inhibitor---0.2～0.6%;
(5) lubrication dispersing agent---1～3%;
(6) coupling agent---0.2～1.5%
2. the preparation method is following:
(1) resin drying: the PBT resin 120～140 ℃ dry 4～6 hours down, moisture controlled is below 0.3%, dry back is subsequent use;
(2) fire retardant pre-treatment: the halogen-free phosphorus-free inflaming retarding agent is carried out surface-active-treatment with coupling agent being not less than under 1000 rev/mins the high-speed stirring, and dry back is subsequent use;
(3) mix: dried PBT resin, halogen-free phosphorus-free inflaming retarding agent, toughner, oxidation inhibitor, lubrication dispersing agent after step (2) is handled are mixed with impeller or get into the premix machine through the metering feeding device separately;
(4) melt extrude granulation: above-mentioned compound is added in the twin screw extruder; The adjusting engine speed is 180～350rpm, and the feeding rotating speed is 250～800rpm, melt extrudes temperature in 160～250 ℃ of scopes; Under the conveying and shearing action of twin screw extruder; Fully fusion plastification, mediate mixing, water ring pelletizing or cold drawn pelletizing through head is extruded after, dry back packing promptly gets PBT special use halogen-free phosphorus-free inflaming retarding plasticizing mother particle.
Related content is explained as follows in the technique scheme:
(1) in the such scheme, said halogen-free phosphorus-free inflaming retarding agent is for gathering thio-phenyl phosphonic acids (9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphono) penylene ester (PDPTP);
(2) in the such scheme, said toughner is POE, ethylene-butyl acrylate copolymer, new LDPE (film grade) of GMA grafted POE, maleic anhydride graft etc.;
(3) in the such scheme, said oxidation inhibitor is the compound antioxidant system that 1010/168 oxidation inhibitor is formed;
(4) in the such scheme, said lubrication dispersing agent is polyethylene wax, Poly Propylene Wax, EBS, TAF etc.;
(5) in the such scheme, said coupling agent is silane coupling agent, titanate coupling agent.
Know-why of the present invention is following:
The present invention is a halogen-free flame retardants to gather thio-phenyl phosphonic acids (9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphono) penylene ester (PDPTP), can play good flame-retardant effect to the PBT material.Its principle is that PDPTP decomposes the non-ignitibility liquid film that generates phosphoric acid when burning, and its boiling point can reach 300 ℃.Simultaneously, phosphoric acid further dewaters again and generates metaphosphoric acid, and the further polymerization of metaphosphoric acid generates and gathers metaphosphoric acid.In this process, the tectum that is not only generated by phosphoric acid plays coating effect, and because the metaphosphoric acid that gathers that generates is a strong acid; It is very strong dewatering agent; Make the polymkeric substance dehydration and charing, changed the pattern of polymer combustion process, reduced the inflammable gas quantity that the polymkeric substance thermolysis produces; And form carbon film with secluding air and heat, thereby the very strong flame retardant effect of performance on its surface.In addition, PDPTP also is a kind of radical scavenger, has PO to form during burning, can combine with the Wasserstoffatoms in the flame region, plays the effect that suppresses flame, thereby better plays fire retardation.
The present invention is halogen-free flame retardants with PDPTP, and this fire retardant itself is exactly a high molecular polymer, and the organic group on the flame retardant molecule and PBT have consistency preferably; Do not separate out; " frosting phenomenon " can not occur, pass through the coupling agent surface modification treatment again, consistency is further improved; Flame retarding efficiency can be improved, the PBT mechanical property can be improved again.The present invention does carrier with PBT, has added the toughner that has the compatilizer effect concurrently again, and the pulvis that halogen-free flame retardants is such is made master batch, and following beneficial effect is arranged: the consistency that has guaranteed master batch and PBT resin; Significantly reduce dust, improved the production operation environment of PBT modification; Secondary disperses can to make fire retardant in following process, obtain preferably, and when improving flame retardant effect, toughness also increases, and has guaranteed the mechanical property of material.
Products characteristics of the present invention:
1) this product good flame retardation effect can make the PBT Flame Retardancy reach U.S. UL94 0.8mm V-0 level.
2) can significantly improve the mechanical property of modified PBT plastic material.
3) the PBT material anti creepage trace index (CTI) after the modification is reached more than the 425V.
4) can make PBT material glowing filament (GWIT) test temperature after the modification reach 750 ℃ not on fire.
5) non-phosphorus is, does not influence color matching fully.
6) satisfy ROHS of European Union and Reach statutory standard, all restricted substances detect the index result and are ND (promptly not detecting this restricted substances).
7) not containing halide (F, Cl, Br, I) and phosphorus flame retardant satisfy the non-halogen standard of IEC.
8) when the plastic material modification is used, there is not dust to produce, non-environmental-pollution harm.
9) can directly when injection moulding, use.
Description of drawings
Accompanying drawing 1 is process flow sheet of the present invention.
Embodiment
Referring to shown in Figure 1, the preparation method is following:
(1) resin drying: the PBT resin 120～140 ℃ dry 4～6 hours down, moisture controlled is below 0.03%, dry back is subsequent use;
(2) fire retardant pre-treatment: the halogen-free phosphorus-free inflaming retarding agent is carried out surface-active-treatment with coupling agent being not less than under 1000 rev/mins the high-speed stirring, and dry back is subsequent use;
(3) mix: dried PBT resin, halogen-free phosphorus-free inflaming retarding agent, toughner, oxidation inhibitor, lubrication dispersing agent after step (2) is handled are mixed with impeller or get into the premix machine through the metering feeding device separately;
(4) melt extrude granulation: above-mentioned compound is added in the twin screw extruder; The adjusting engine speed is 180～350rpm, and the feeding rotating speed is 250～800rpm, melt extrudes temperature in 180～250 ℃ of scopes; Under the conveying and shearing action of twin screw extruder; Fully fusion plastification, mediate mixing, water ring pelletizing or cold drawn pelletizing through head is extruded after, dry back packing promptly gets PBT special use halogen-free phosphorus-free inflaming retarding plasticizing mother particle.
According to above-mentioned preparation method:
Embodiment 1
The special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle prescription of PBT (weight percentage)
(1) PBT resin---40%;
(2) halogen-free phosphorus-free inflaming retarding agent---50%;
(3) GMA grafted POE---7.5%;
The compound antioxidant system that (4) 1010,168 oxidation inhibitor are formed---0.4%;
(5) polyethylene wax---1.5%;
(6) silane coupling agent---1%
This master batch is used for the PBT modification, adds 30～35% and can reach UL940.8mm V0
Embodiment 2
The special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle prescription of PBT (weight percentage)
(1) PBT resin---30%;
(2) halogen-free phosphorus-free inflaming retarding agent---58%;
(3) ethylene-butyl acrylate copolymer and new LDPE (film grade)---9%;
The compound antioxidant system that (4) 1010,168 oxidation inhibitor are formed---0.5%;
(5) lubricating system of polyethylene wax and EBS composition---2%;
(6) silane coupling agent---1.5%
This master batch is used for the PBT modification, adds 25～30% and can reach UL940.8mm V0
Embodiment 3
The special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle prescription of PBT (weight percentage)
(1) PBT resin---52%;
(2) halogen-free phosphorus-free inflaming retarding agent---40%;
(3) POE of maleic anhydride graft---6%;
The compound antioxidant system that (4) 1010,168 oxidation inhibitor are formed---0.3%;
(5) Poly Propylene Wax and TAF lubricating system---1%;
(6) titanate coupling agent---0.6%
This master batch is used for the PBT modification, adds 35～45% and can reach UL94 0.8mm V0
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (8)
1. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of a PBT, it is characterized in that: composition of raw materials is (percentage ratio by weight):
(1) PBT resin---20～60%;
(2) halogen-free phosphorus-free inflaming retarding agent---70～35%;
(3) toughner---5～10%;
(4) oxidation inhibitor---0.2～0.6%;
(5) lubrication dispersing agent---1～3%;
(6) coupling agent---0.2～1.5%
2. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1 is characterized in that said halogen-free phosphorus-free inflaming retarding agent is for gathering thio-phenyl phosphonic acids (9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphono) penylene ester (PDPTP).
3. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1 is characterized in that said toughner is the POE, ethylene-butyl acrylate copolymer, new LDPE (film grade) of GMA grafted POE, maleic anhydride graft etc.
4. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1 is characterized in that said oxidation inhibitor is the compound antioxidant system that 1010,168 oxidation inhibitor are formed.
5. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1 is characterized in that said lubrication dispersing agent is polyethylene wax, Poly Propylene Wax, EBS, TAF etc.
6. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1 is characterized in that said coupling agent is silane coupling agent, titanate coupling agent.
7. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 1, it is characterized in that: the preparation method is following:
(1) resin drying: the PBT resin 120～140 ℃ dry 4～6 hours down, moisture controlled is below 0.3%, dry back is subsequent use;
(2) fire retardant pre-treatment: the halogen-free phosphorus-free inflaming retarding agent is carried out surface-active-treatment with coupling agent being not less than under 1000 rev/mins the high-speed stirring, and dry back is subsequent use;
(3) mix: dried PBT resin, the agent of composite halogen-free phosphorus-free flame-retarding, toughner, oxidation inhibitor, lubrication dispersing agent after step (2) is handled are mixed with impeller or get into the premix machine through the metering feeding device separately;
(4) melt extrude granulation: above-mentioned compound is added in the twin screw extruder; The adjusting engine speed is 180～350rpm, and the feeding rotating speed is 250～800rpm, melt extrudes temperature in 180～250 ℃ of scopes; Under the conveying and shearing action of twin screw extruder; Fully fusion plastification, mediate mixing, water ring pelletizing or cold drawn pelletizing through head is extruded after, dry back packing promptly gets PBT special use halogen-free phosphorus-free inflaming retarding plasticizing mother particle.
8. the special-purpose halogen-free phosphorus-free inflaming retarding plasticizing mother particle of PBT according to claim 8 preparation method is characterized in that the fire retardant pretreatment process is described in the step (2): carry out surface-active-treatment with coupling agent being not less than under 1000 rev/mins the high-speed stirring.
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| CN2012100319766A CN102532830A (en) | 2012-02-14 | 2012-02-14 | Halogen-free phosphorus-free flame-retarding toughening master batch special for PBT (polybutylene terephthalate) and preparation method thereof |
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| CN2012100319766A CN102532830A (en) | 2012-02-14 | 2012-02-14 | Halogen-free phosphorus-free flame-retarding toughening master batch special for PBT (polybutylene terephthalate) and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820490A (en) * | 2016-02-19 | 2016-08-03 | 宁波能之光新材料科技有限公司 | PBT toughening master batch and preparation method thereof |
| CN113754902A (en) * | 2021-09-30 | 2021-12-07 | 浙江新化化工股份有限公司 | Environment-friendly polyamide flame-retardant master batch and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798447A (en) * | 2010-03-19 | 2010-08-11 | 苏州兰特纳米材料科技有限公司 | PBT (Polybutylece Terephthalate) special halogen and phosphorus free inflaming retarding plasticizing mother particle and preparation method thereof |
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- 2012-02-14 CN CN2012100319766A patent/CN102532830A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798447A (en) * | 2010-03-19 | 2010-08-11 | 苏州兰特纳米材料科技有限公司 | PBT (Polybutylece Terephthalate) special halogen and phosphorus free inflaming retarding plasticizing mother particle and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820490A (en) * | 2016-02-19 | 2016-08-03 | 宁波能之光新材料科技有限公司 | PBT toughening master batch and preparation method thereof |
| CN113754902A (en) * | 2021-09-30 | 2021-12-07 | 浙江新化化工股份有限公司 | Environment-friendly polyamide flame-retardant master batch and preparation method thereof |
| CN113754902B (en) * | 2021-09-30 | 2023-10-03 | 浙江新化化工股份有限公司 | Environment-friendly polyamide flame-retardant master batch and preparation method thereof |
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Application publication date: 20120704 |