CN103772919A - Halogen-free fire-retardant glass fiber reinforced PET composition and preparation method thereof - Google Patents
Halogen-free fire-retardant glass fiber reinforced PET composition and preparation method thereof Download PDFInfo
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- CN103772919A CN103772919A CN201210393487.5A CN201210393487A CN103772919A CN 103772919 A CN103772919 A CN 103772919A CN 201210393487 A CN201210393487 A CN 201210393487A CN 103772919 A CN103772919 A CN 103772919A
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- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention belongs to the field of engineering plastics, and relates to a glass fiber reinforced PET composition and a preparation method thereof. The composition is prepared from the following components in parts by weight: 100 parts of polyethylene glycol terephthalate, 5-25 parts of a halogen-free flame retardant agent, 20-100 parts of glass fiber, 1-5 parts of a nucleating agent, 0.1-0.5 part of an antioxidant, 1-3 parts of a lubrication modifier, and 0.1-0.2 part of a coupling agent. The polyethylene terephthalate can be allowed to obtain quite good flame-retardant property under a condition of quite small reduction amplitude of mechanical properties, and the composition has the characteristics of simple formula, simple and easily implemented process, good processing formability and good surface appearance, and allows products to be easy to demould.
Description
Technical field
The invention belongs to engineering plastics field, relate to a kind of glass REINFORCED PET composition and method of making the same.
Background technology
Polyethylene terephthalate (PET) is the material that a kind of performance is very excellent, because it has good mechanical property, and good tint permanence, chemical resistance etc., thereby be widely used in building trade, automobile industry, electric utility.But because PET is the one macromolecular material that can burn, limiting oxygen index(LOI), at 21-23, belongs to inflammable or flammable macromolecular material in classification, and easily produces drippage in the time of burning, cause the serious consequence of fire spreading, therefore seriously limited the application of PET in industry-by-industry.
For a long time, what on market, most Flame-Retarded PET Engineering Plastics used is the fire retardant that has halogen, it is mainly the fire retardant of bromine system, comprise decabromodiphynly oxide, octabromodiphenyl ether, tetrabromo-bisphenol etc., these fire retardants have advantages of that good flame retardation effect, addition are few, it is little that resin matrix mechanical property is affected, thereby use very extensive.But, there is halogen fire retardant can decomposes go out a large amount of harmful hydrogen halides in the time of burning, very easily human body is caused to secondary injury, in view of there being toxicity and the environmental protection reason of halogen fire retardant, European Union has promulgated WEEE and two instructions of RoHS for 2003, to there being the use of halogen fire retardant to make strict restriction.Therefore, exploitation halogen-free flameproof PET not only has huge economic worth, grows with each passing hour especially, realizes the inevitable requirement of Sustainable development.
Summary of the invention
The PET composition and method of making the same that an object of the present invention is to provide a kind of halogen-free flameproof modification, the method is carried out halogen-free flameproof modification to PET, can make fiber glass reinforced halogen-free flame retardant PET engineering plastics.
For achieving the above object, the present invention is by the following technical solutions:
A kind of glass REINFORCED PET composition, made by the component that comprises following weight part:
100 parts of polyethylene terephthalates (PET),
Halogen-free flame retardants 5-25 part,
Glass fibre 20-100 part,
Nucleator 1-5 part,
Oxidation inhibitor 0.1-0.5 part
Lubricating modification agent 1-3 part,
Coupling agent 0.1-0.2 part.
Described polyethylene terephthalate (PET) is intrinsic viscosity 0.65-0.82dl/g; It is fast that this range of viscosities has crystallization rate, and the feature of good processability is used this range of viscosities PET can make composition of the present invention have good mechanical property and machine-shaping property.
Described halogen-free flame retardants is selected from one or more in benzoguanamine (BG), phosphorous thermotropic liquid crystal high polymer (TLCP) or six (4-nitrophenoxys) ring tripolyphosphazenes (HNCP).
Described glass fibre is surface treated continuous glass fibre, and preferably megalith group produces the continuous glass fibre of 988 continuous glass fibres, 988A continuous glass fibre or three kinds of trades mark of 990 continuous glass fibres.
Described nucleator is that surlyn resin nucleating agent, nano-attapulgite organic-inorganic are re-dubbed the amorphous powder of nuclear system or surface organic processing and the composite organic system of small molecules polymkeric substance of grafting.
Described nucleator is preferably the surlyn resin of Du Pont's product trade mark 8920.
Described nano-attapulgite organic-inorganic is re-dubbed the preferred Jiangsu of nuclear system nine river nanosecond science and technology company limited and produces trade mark MT502A nucleator; The special nucleator of PET of the composite preferred commercially available trade mark ADD301 of organic system of the amorphous powder of described surface organic processing and the small molecules polymkeric substance of grafting.
Described oxidation inhibitor is alkyl Polyphenols oxidation inhibitor, preferably by four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (irgasfos 168) with the composite compound antioxidant forming of weight ratio 1:1.
Described lubricating modification agent is silicone powder, and preferably Yuyao Kai Mulihua plastic cement Science and Technology Ltd. sells SK20R silicone powder.
Described coupling agent is silane coupling agent, titante coupling agent, preferably γ-aminopropyl triethoxysilane (Silane coupling agent KH550).
A preparation method for above-mentioned glass REINFORCED PET composition, comprises the following steps:
(1) raw material mixes
Polyethylene terephthalate (PET), halogen-free flame retardants are placed in after 80-120 ℃ of baking oven oven dry, take each component raw material of following weight part by said ratio, 100 parts of polyester PETs, halogen-free flame retardants 5-25 part, glass fibre 20-100 part, nucleator 1-5 part, oxidation inhibitor 0.1-0.5 part, lubricating modification agent 1-3 part, coupling agent 0.1-0.2 part; Polyester PET, halogen-free flame retardants and nucleator, oxidation inhibitor, lubricating modification agent, coupling agent are joined in high mixer, and continuous high speed stirs about 5 minutes at normal temperatures, mixes;
(2) extruding pelletization
The raw mixture obtaining in step (1) is joined in the hopper of twin screw extruder, add entrance at the glass of twin screw extruder and be involved in continuous glass-fiber, melt extrude granulation simultaneously; Obtain halogen-free flameproof PET composition of the present invention.
In described step (2), expressing technique is as follows: from spout to head, totally ten sections of extrusion temperatures are respectively 190 ~ 230 ℃, 250 ~ 260 ℃, 250 ~ 260 ℃, 245 ~ 255 ℃, 245 ~ 255 ℃, 240 ~ 250 ℃, 240 ~ 250 ℃, 250 ~ 260 ℃, 250 ~ 260 ℃, 255 ~ 265 ℃, and head temperature is 260 ~ 270 ℃; Screw speed is 250 ~ 300r/min.
The present invention has following beneficial effect:
The present invention can make polyethylene terephthalate (PET) obtain in the case of the very little amplitude of mechanical property decline
It is simple that well flame retardant properties, and the present invention has formula, and simple process is easily gone, and machine-shaping property is good, the easy demoulding of goods, apparent good feature.
Embodiment
Below in conjunction with specific embodiment, Method and process involved in the present invention is described, the following example only, for operating process of the present invention and formula are described, does not limit protection scope of the present invention.
The PET resin that polyethylene terephthalate (PET) in embodiment 1-9 is SB500 for the Yizheng petrochemical industry product trade mark, intrinsic viscosity 0.65dl/g; Oxidation inhibitor is that antioxygen 1010 and antioxygen 168 are with the composite compound antioxidant forming of weight ratio 1:1; Described glass fibre is the glass that megalith group produces, and comprises that the trade mark is 988; Nucleator is the surlyn resin that Du Pont produces the trade mark 8920; Silicone powder is that Yuyao Kai Mulihua plastic cement Science and Technology Ltd. sells SK20R silicone powder.
Embodiment 1-9
(1) by polyethylene terephthalate (PET), halogen-free flame retardants is placed in after 80-120 ℃ of baking oven oven dry, by polyester PET, halogen-free flame retardants, nucleator, oxidation inhibitor, lubricating modification agent, coupling agent is pressed after formula metering, join in high mixer, continuous high speed stirs 5 minutes at normal temperatures, the raw mixture that obtains mixing, wherein in polyester PET 100 weight parts, halogen-free flame retardants 5-25 weight part, glass 20-100 weight part, nucleator 1-5 weight part, oxidation inhibitor 0.1-0.5 weight part, lubricating modification agent 1-3 weight part, coupling agent 0.1-0.2 part, the concrete formulation parameter of embodiment 1-9 is in table 1,
(2) then the raw mixture obtaining in step (1) is joined in the hopper of twin screw extruder, add entrance at glass and add continuous glass-fiber, according to above-mentioned expressing technique extruding pelletization simultaneously.Obtain halogen-free flameproof PET composition of the present invention.
Wherein, in step (2), forcing machine is the not parallel dual-screw extruding machine of the product model TSE-35A of this extra-high-speed polymers equipment company limited of Nanjing Rhea, this extruder screw nominal screw rod 35mm, length-to-diameter ratio 44, rotating speed 60-600r/min.
The described injection moulding machine of step (3) is that Zhen De plastics machinery Co., Ltd., Factory manufactures model C J80M2V plastic-injection moulding machine, Shooting Technique is 245 ~ 250 ℃ of one section of temperature, injection speed 50 ~ 99%, 250 ~ 255 ℃ of pressure 99 ~ 88%, two sections of temperature, injection speed 45 ~ 88%, pressure 88 ~ 77%, three sections of 245 ~ 250 ℃ of temperature, injection speed 40 ~ 77%, pressure 77 ~ 66%, pressurize for some time 6 ~ 8S, pressure 40 ~ 50%, two sections of time 4 ~ 6S of pressurize, pressure 50 ~ 60%; Cooling time 6 ~ 8S, 90 ~ 120 ℃ of die temperatures.
In the baking oven of 80-120 ℃, dry 6-10 hour by obtaining pellet in step (2), be then injection molded into ASTM standard batten.Carry out mechanical property and combustionproperty test.Testing standard and performance data are in table 2.
Comparative example 1-3
Polyethylene terephthalate (PET), nucleator, oxidation inhibitor, lubricating modification agent, coupling agent are pressed after formula metering, join in high mixer, continuous high speed stirs about 5 minutes at normal temperatures, the raw mixture that obtains mixing, wherein in polyester PET 100 weight parts, glass 20-100 weight part, nucleator 1-5 weight part, oxidation inhibitor 0.1-0.5 weight part, lubricating modification agent 1-3 weight part, coupling agent 0.1-0.2 part.Then raw mixture is joined in the hopper of twin screw extruder, add entrance at glass and add continuous glass-fiber, according to above-mentioned expressing technique extruding pelletization simultaneously.The concrete formulation parameter of comparative example 1-3 is in table 1.
Above-mentioned pellet is dried to 6-10 hour in the baking oven of 80-120 ℃, then according to above-mentioned Shooting Technique injection moulding standard batten, carry out mechanical property and combustionproperty test, testing standard and performance data are in table 2.
Table 1
Table 2
| Tensile strength/Mpa | Flexural strength/Mpa | Fire-retardant rank | |
| Testing standard | ASTM | ASTM | UL-94 |
| Embodiment 1 | 94.4 | 112.6 | 3.2mm?V-2 |
| Embodiment 2 | 95.7 | 118.6 | 3.2mmV1 |
| Embodiment 3 | 108.8 | 155.9 | 3.2mm?V-0 |
| Embodiment 4 | 125.2 | 189.4 | 3.2mmV1 |
| Embodiment 5 | 153.9 | 227.5 | 3.2mm?V-0 |
| Embodiment 6 | 120 | 183.1 | 3.2mm?V-0 |
| Embodiment 7 | 96.3 | 117.2 | 3.2mmV1 |
| Embodiment 8 | 105.9 | 158.7 | 3.2mm?V-0 |
| Embodiment 9 | 118.6 | 179.6 | 3.2mm?V-0 |
| Comparative example 1 | 99.1 | 122.9 | Not?rated |
| Comparative example 2 | 114.5 | 160.3 | Not?rated |
| Comparative example 3 | 137.2 | 201.6 | Not?rated |
Associative list 1 and table 2 can find out, the embodiment that has added halogen-free flame retardants declines very little amplitude and obtained good flame retardant properties in mechanical property.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a glass fiber reinforced polyethylene terephthalate composition, is characterized in that: be made up of the component that comprises following weight part:
100 parts of polyethylene terephthalates,
Halogen-free flame retardants 5-25 part,
Glass fibre 20-100 part,
Nucleator 1-5 part,
Oxidation inhibitor 0.1-0.5 part
Lubricating modification agent 1-3 part,
Coupling agent 0.1-0.2 part.
2. glass fiber reinforced polyethylene terephthalate composition according to claim 1, is characterized in that: described polyethylene terephthalate is intrinsic viscosity 0.65-0.82dl/g.
3. glass fiber reinforced polyethylene terephthalate composition according to claim 1, is characterized in that: described halogen-free flame retardants is selected from one or more in benzoguanamine, phosphorous thermotropic liquid crystal high polymer or six (4-nitrophenoxy) ring tripolyphosphazene.
4. glass fiber reinforced polyethylene terephthalate composition according to claim 1, it is characterized in that: described glass fibre is surface treated continuous glass fibre, preferably 988 continuous glass fibres, 988A continuous glass fibre or 990 continuous glass fibres.
5. glass fiber reinforced polyethylene terephthalate composition according to claim 1, is characterized in that: described nucleator is that surlyn resin nucleating agent, nano-attapulgite organic-inorganic are re-dubbed the amorphous powder of nuclear system or surface organic processing and the composite organic system of small molecules polymkeric substance of grafting.
6. glass fiber reinforced polyethylene terephthalate composition according to claim 5, is characterized in that: described nucleator is the surlyn resin that Du Pont produces the trade mark 8920;
Or described nano-attapulgite organic-inorganic is re-dubbed the preferred MT502A nucleator of nuclear system;
Or the special nucleator of PET of the amorphous powder of described surface organic processing and the composite preferred ADD301 of organic system of the small molecules polymkeric substance of grafting.
7. glass fiber reinforced polyethylene terephthalate composition according to claim 1, it is characterized in that: described oxidation inhibitor is alkyl Polyphenols oxidation inhibitor, preferably by four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester with the composite compound antioxidant forming of weight ratio 1:1.
8. glass fiber reinforced polyethylene terephthalate composition according to claim 1, is characterized in that: described lubricating modification agent is silicone powder;
Or described coupling agent is silane coupling agent, titante coupling agent, preferred silane coupling agent γ-aminopropyl triethoxysilane.
9. a preparation method for arbitrary described glass fiber reinforced polyethylene terephthalate composition in the claims 1-8, is characterized in that: comprise the following steps:
(1) raw material mixes
Polyethylene terephthalate (PET), halogen-free flame retardants are placed in after 80-120 ℃ of baking oven oven dry, take each component raw material of following weight part by said ratio, 100 parts of polyester PETs, halogen-free flame retardants 5-25 part, glass fibre 20-100 part, nucleator 1-5 part, oxidation inhibitor 0.1-0.5 part, lubricating modification agent 1-3 part, coupling agent 0.1-0.2 part; Polyethylene terephthalate, halogen-free flame retardants and nucleator, oxidation inhibitor, lubricating modification agent, coupling agent are joined in high mixer, and continuous high speed stirs about 5 minutes at normal temperatures, mixes;
(2) extruding pelletization
The raw mixture obtaining in step (1) is joined in the hopper of twin screw extruder, add entrance at the glass of twin screw extruder and be involved in continuous glass-fiber, melt extrude granulation simultaneously; Obtain glass fiber reinforced polyethylene terephthalate composition of the present invention.
10. preparation method according to claim 9, it is characterized in that: in described step (2), expressing technique is as follows: from spout to head, totally ten sections of extrusion temperatures are respectively 190 ~ 230 ℃, 250 ~ 260 ℃, 250 ~ 260 ℃, 245 ~ 255 ℃, 245 ~ 255 ℃, 240 ~ 250 ℃, 240 ~ 250 ℃, 250 ~ 260 ℃, 250 ~ 260 ℃, 255 ~ 265 ℃, and head temperature is 260 ~ 270 ℃; Screw speed is 250 ~ 300r/min.
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