CN104371162A - Flame-retardant wear-resisting modified polypropylene material and preparation method thereof - Google Patents
Flame-retardant wear-resisting modified polypropylene material and preparation method thereof Download PDFInfo
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- CN104371162A CN104371162A CN201410060002.XA CN201410060002A CN104371162A CN 104371162 A CN104371162 A CN 104371162A CN 201410060002 A CN201410060002 A CN 201410060002A CN 104371162 A CN104371162 A CN 104371162A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The present invention relates to a flame-retardant wear-resisting modified polypropylene material which comprises the following raw materials by weight: 100 parts of polyethylene, 10-100 parts of acicular wollastonite, 10-30 parts of a flame retardant, 10-50 parts of glass fiber, 0.01-0.5 part of an acid removing agent, 0.2-0.5 part of an antioxidant, 0.1-1 part of a light stabilizer, 0.1-0.7 part of a compatible agent, and 0.1-0.3 part of a lubricant; and the present invention provides a preparation method of the modified polyethylene material. The flame-retardant wear-resisting modified polypropylene material uses the acicular wollastonite as an anti dripping agent of the flame retardant and the glass fiber as a filling reinforcing agent, and improves the fire retardant properties, mechanical properties and wear resistance of the material.
Description
Technical field
The invention belongs to processing of high molecular material technical field, especially relate to a kind of fire-retardant, wear-resisting modified polyethylene material and preparation method thereof.
Background technology
Polyethylene, because its density is little, price is low, processing forming is good and the advantage such as high comprehensive performance, is widely used in the inside and outside gadget of automobile and electronics device shell etc., is to use one of maximum thermoplastics at present.But due to poly resistance toheat and rigidity lower, need by add talcum powder, glass fibre etc. improve its thermotolerance and mechanical property by modification.
Along with the development of modern science and technology, people are also more and more stricter to poly flame-retardancy requirements, require that it reaches certain flame-retardancy requirements, as: the V0 rank of UL-94 or higher category.With regard to current polymer flame retardant, mainly contain that Halogen is fire-retardant, the large class of halogen-free flameproof two.In practical study and application, in order to while reaching desirable flame retardant effect, also to reduce the consumption of main flame retardant, add anti-dripping agent and the composite use of main flame retardant often in the polymer, good effect can be played like this.Current anti-dripping agent is almost PTFE Type anti-dripping agent on the market entirely.
The main component of wollastonite is Calucium Silicate powder, and white crystals has beta crystal, becomes the mixture of needle-like, the various form particle such as bar-shaped and granular.And acicular wollastonite has larger length-to-diameter ratio, be mainly used for filling and strengthen polymkeric substance, and content is high is generally 5%-50%.Such as: Chinese patent CN 103059415 A, uses acicular wollastonite as weighting material, and consumption is up to the number identical with matrix resin polypropylene.
In addition, Chinese patent CN102532692A discloses a kind of Wollastonite modified polypropylene composite material, employing length-to-diameter ratio is that the wollastonite of 3:1-20:1 carries out filling-modified to polypropylene, significantly improve the anti-slungshot impact property of polypropylene material, but cause the mechanical property of wollastonite/polypropylene composite material not high due to the poor compatibility between wollastonite and polypropylene.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of fire-retardant, wear-resisting modified polyethylene material and preparation method thereof is provided, modified polyethylene material not only has excellent mechanical property, and crocking resistance is excellent.
Technical scheme of the present invention is as follows:
Fire-retardant, a wear-resisting modified polyethylene material, is characterized in that: be prepared from by weight by following raw material:
Polyethylene 100 parts;
Acicular wollastonite 10-100 part;
Fire retardant 10-30 part;
Glass fibre 10-50 part;
Acid scavenger 0.01-0.5 part;
Oxidation inhibitor 0.2-0.5 part;
Light steady agent 0.1-1 part;
Compatilizer 0.1-0.7 part;
Lubricant 0.1-0.3 part.
Described fire retardant select in TDE, eight bromine S ethers, antimonous oxide, Halogen nitrogen phosphorus fire retardant one or both.
The length-to-diameter ratio of described acicular wollastonite is 7:1 ~ 22:1, particle diameter is 600 order ~ 1250 orders; Described glass fibre is alkali free glass fibre, and its diameter is 8-15um.
Described acid scavenger is calcium oxide, zinc oxide or hydrotalcite.
Described oxidation inhibitor by primary antioxidant and secondary oxidation inhibitor in mass ratio 1:2-1:1 form; described primary antioxidant is N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) or four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010), secondary oxidation inhibitor is three (2.4-di-tert-butyl-phenyl) phosphorous acid ester (irgasfos 168).
Described photostabilizer is two (2,2,6,6-tetramethyl-piperidyl) sebate (be called for short light steady agent 770) or poly-{ [6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-bis-base] [2-(2,2,6,6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] (being called for short the steady agent 944 of light).
Described compatilizer is at least one in polypropylene grafted maleic anhydride (PP-g-MAH), polypropylene grafted glycidyl methacrylate (PP-g-GMA), grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH), terpolymer EP rubber graft glycidyl methacrylate (EPDM-g-GMA).
Described lubricant is whiteruss, ethylene bis stearamide or butyl stearate.
Another object of the present invention is to provide a kind of method preparing above-mentioned fire-retardant, wear-resisting modified polyethylene material, comprises the following steps:
(1) each raw material is taken by weight;
(2) glass fibre is mixed with acid scavenger;
(3) by polyethylene, fire retardant, acicular wollastonite, oxidation inhibitor, the steady agent of light, compatilizer, lubricant in high mixer mixing 1-3min;
(4) mixture in (3) is added the twin screw extruder that temperature is 170-220 DEG C, rotating speed is 150-300 rev/min, the mixture of (2) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
The present invention compared with prior art, has following beneficial effect:
1, acid scavenger is adopted to be the material that the alkaline stronger persistence of a class consumes free acid in the present invention, effectively can remove the free acid in modified polyethylene material and the sour environment in change system, thus make matrix material present neutrality or weakly alkaline, thus improve the weathering resistance of material.And the antagonistic action eliminated between the steady agent of light and compatilizer, thus improve mechanical property and the weather resistance of modified polyethylene material.
2, the present invention is using the anti-dripping agent use of acicular wollastonite as fire retardant, and glass fibre uses as filling toughener, improves its mechanical property while improve the flame retardant properties of material.
3, the alkali free glass fibre of described glass fibre to be diameter be 8-15um, adds forcing machine by the mode of side feeding, can reduce the destruction of screw rod to glass fibre.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Frictional wear experiment method (according to standard GB/T 3960-83)
Friction wear testing machine model: MM-200;
Lubricating condition: metal to-metal contact;
Envrionment conditions: 60 DEG C;
Test pressure: 150N;
Test period: 90min;
Lower sample material: 45# steel;
Lower sample rotation rate: 200r/min;
Batten size: L30mm W7mm H6mm.
Flame retardant test: undertaken testing respective flame resistance performance by UL-94 standard, and compare the t1+t2(second of 5 battens) the summation time.
Embodiment 1
(1) 0.01 part, 10 parts, glass fibre and acid scavenger calcium oxide is mixed;
(2) by polyethylene 100 parts, fire retardant Halogen nitrogen phosphorus fire retardant 10 parts, acicular wollastonite 1 part, 1,098 0.1 parts, oxidation inhibitor, irgasfos 168 0.1 part, the steady agent of light 770 1 parts, Compatibilizer PP-g-MAH 1 part, lubricant stearic acid butyl ester 0.3 part in high mixer mixing 1-3min;
(3) mixture in (2) is added the twin screw extruder that each district temperature is 170-220 DEG C, rotating speed is 150 revs/min, the mixture of (1) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
Embodiment 2
(1) 0.05 part, 20 parts, glass fibre and acid scavenger zinc oxide is mixed;
(2) by polyethylene 100 parts, TDE 10 parts, acicular wollastonite 0.5 part, antioxidant 1010 0.1 part, irgasfos 168 0.2 part, the steady agent of light 944 0.5 parts, compatilizer PP-g-GMA 3 parts, 0.2 part, lubricating fluid paraffin in high mixer mixing 1-3min;
(3) mixture in (2) is added the twin screw extruder that each district temperature is 170-220 DEG C, rotating speed is 200 revs/min, the mixture of (1) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
Embodiment 3
(1) 30 parts, glass fibre and acid scavenger hydrotalcite 0.1 part is mixed;
(2) by polyethylene 100 parts, 15 parts, fire retardant eight bromine S ether, acicular wollastonite 1 part, 1098 parts 0.2 part, oxidation inhibitor, irgasfos 168 0.2 part, the steady agent of light 770 0.1 parts, compatilizer EPDM-g-MAH 3 parts, EPDM-g-GMA 4 parts, lubricant stearic acid butyl ester) 0.1 part in high mixer mixing 1-3min;
(3) mixture in (2) is added the twin screw extruder that each district temperature is 170-220 DEG C, rotating speed is 250 revs/min, the mixture of (1) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
Embodiment 4
(1) 0.2 part, 40 parts, glass fibre and acid scavenger calcium oxide is mixed;
(2) by polyethylene 100 parts, fire retardant antimonous oxide 20 parts, acicular wollastonite 1.5 parts, 1,098 0.15 parts, oxidation inhibitor, irgasfos 168 0.3 part, the steady agent of light 944 0.3 parts, compatilizer EPDM-g-GMA 5 parts, lubricant ethylene bis stearamide 0.1 part in high mixer mixing 1-3min;
(3) mixture in (2) is added the twin screw extruder that each district temperature is 170-220 DEG C, rotating speed is 300 revs/min, the mixture of (1) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
Embodiment 5
(1) 50 parts, glass fibre and acid scavenger hydrotalcite 0.5 part is mixed;
(2) by polyethylene 100 parts, TDE 10 parts, eight 10 parts, bromine S ethers, acicular wollastonite 2 parts, antioxidant 1010 0.25 part, irgasfos 168 0.25 part, the steady agent of light 944 0.1 parts, Compatibilizer PP-g-MAH 1 part, PP-g-GMA 2 parts, 0.3 part, lubricating fluid paraffin in high mixer mixing 1-3min;
(3) mixture in (2) is added the twin screw extruder that each district temperature is 170-220 DEG C, rotating speed is 300 revs/min, the mixture of (1) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
The modified polyethylene material prepared by embodiment 1-5 is injection molded into GB batten according to unified technique, carries out mechanical property respectively and flame retardant properties is tested according to testing standard listed in table 1 and condition to it:
Table 1 the performance test results
As can be seen from the above table: the glass fibre added in polyethylene through acid scavenger improvement obtains modified polyethylene material, the tensile strength of its material, flexural strength, modulus in flexure, simply supported beam notched Izod impact strength all obtain raising in various degree, and especially modulus in flexure is largely increased; Present invention adds anti-dripping agent acicular wollastonite in addition, improve the flame retardant properties of modified poly ethylene.Namely a kind of good mechanical performance can be prepared by composition and engineering of the present invention, rub resistance and the good modified polyethylene material of flame retardant properties.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. fire-retardant, a wear-resisting modified polyethylene material, is characterized in that: be prepared from by weight by following raw material:
Polyethylene 100 parts;
Acicular wollastonite 10-100 part;
Fire retardant 10-30 part;
Glass fibre 10-50 part;
Acid scavenger 0.01-0.5 part;
Oxidation inhibitor 0.2-0.5 part;
Light steady agent 0.1-1 part;
Compatilizer 0.1-0.7 part;
Lubricant 0.1-0.3 part.
2. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: described fire retardant select in TDE, eight bromine S ethers, antimonous oxide, Halogen nitrogen phosphorus fire retardant one or both.
3. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: the length-to-diameter ratio of described acicular wollastonite is 7:1 ~ 22:1, particle diameter is 600 order ~ 1250 orders; Described glass fibre is alkali free glass fibre, and its diameter is 8-15um.
4. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: described acid scavenger is calcium oxide, zinc oxide or hydrotalcite.
5. fire-retardant, wear-resisting modified polyethylene material according to claim 1; it is characterized in that: described oxidation inhibitor by primary antioxidant and secondary oxidation inhibitor in mass ratio 1:2-1:1 form; described primary antioxidant is N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine or four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, secondary oxidation inhibitor is three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
6. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: described photostabilizer is two (2,2,6,6-tetramethyl-piperidyl) sebate or poly-{ [6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-bis-base] [2-(2,2,6,6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-].
7. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: described compatilizer is at least one in polypropylene grafted maleic anhydride (PP-g-MAH), polypropylene grafted glycidyl methacrylate (PP-g-GMA), grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH), terpolymer EP rubber graft glycidyl methacrylate (EPDM-g-GMA).
8. fire-retardant, wear-resisting modified polyethylene material according to claim 1, is characterized in that: described lubricant is whiteruss, ethylene bis stearamide or butyl stearate.
9. prepare a method for modified polyethylene material fire-retardant, wear-resisting as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) each raw material is taken by weight;
(2) glass fibre is mixed with acid scavenger;
(3) by polyethylene, fire retardant, acicular wollastonite, oxidation inhibitor, the steady agent of light, compatilizer, lubricant in high mixer mixing 1-3min;
(4) mixture in (3) is added the twin screw extruder that temperature is 170-220 DEG C, rotating speed is 150-300 rev/min, the mixture of (2) is added again at the side direction spout of forcing machine, after melt extruding granulation, through water-cooled, pelletizing, namely obtain modified polyethylene material.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774365A (en) * | 2015-04-17 | 2015-07-15 | 柳州蔚园塑料彩印包装有限责任公司 | Wear-resisting engineering plastic |
| CN105741966A (en) * | 2016-05-04 | 2016-07-06 | 江苏亨通线缆科技有限公司 | Metal sheath bureau communication cable for rail transit |
| CN106298001A (en) * | 2016-08-12 | 2017-01-04 | 江苏亨通线缆科技有限公司 | Electromagnetic wave shielding communication cable for track traffic |
| CN106479036A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof |
| CN106479025A (en) * | 2016-10-31 | 2017-03-08 | 江苏昊晟塑业科技有限公司 | Expanded material for automobile door plate |
| CN107286422A (en) * | 2017-06-15 | 2017-10-24 | 东台晨霞新材料科技有限公司 | A kind of high-impact long glass fiber reinforced polyethylene（PE）Composite and preparation method thereof |
| WO2019064203A1 (en) * | 2017-09-28 | 2019-04-04 | Fibre Reinforced Thermoplastics B.V. | Stabilized fiber-containing composite |
| CN109929173A (en) * | 2019-04-02 | 2019-06-25 | 广东胜达塑胶科技有限公司 | A kind of PE tubing of high intensity and preparation method thereof |
| CN112266531A (en) * | 2020-09-24 | 2021-01-26 | 句容市百事特复合材料有限公司 | Low-odor long fiber reinforced polypropylene granule composition and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774365A (en) * | 2015-04-17 | 2015-07-15 | 柳州蔚园塑料彩印包装有限责任公司 | Wear-resisting engineering plastic |
| CN106479036B (en) * | 2015-08-27 | 2020-10-30 | 合肥杰事杰新材料股份有限公司 | Polyolefin composite material for melt lamination rapid molding and preparation method thereof |
| CN106479036A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof |
| CN105741966A (en) * | 2016-05-04 | 2016-07-06 | 江苏亨通线缆科技有限公司 | Metal sheath bureau communication cable for rail transit |
| CN106298001A (en) * | 2016-08-12 | 2017-01-04 | 江苏亨通线缆科技有限公司 | Electromagnetic wave shielding communication cable for track traffic |
| CN106479025A (en) * | 2016-10-31 | 2017-03-08 | 江苏昊晟塑业科技有限公司 | Expanded material for automobile door plate |
| CN107286422A (en) * | 2017-06-15 | 2017-10-24 | 东台晨霞新材料科技有限公司 | A kind of high-impact long glass fiber reinforced polyethylene（PE）Composite and preparation method thereof |
| WO2019064203A1 (en) * | 2017-09-28 | 2019-04-04 | Fibre Reinforced Thermoplastics B.V. | Stabilized fiber-containing composite |
| CN109929173A (en) * | 2019-04-02 | 2019-06-25 | 广东胜达塑胶科技有限公司 | A kind of PE tubing of high intensity and preparation method thereof |
| CN112266531A (en) * | 2020-09-24 | 2021-01-26 | 句容市百事特复合材料有限公司 | Low-odor long fiber reinforced polypropylene granule composition and preparation method thereof |
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Application publication date: 20150225 |