CN106916358A - A kind of high durable flowing glass dipping Polyolefin Formation high and preparation method thereof - Google Patents
A kind of high durable flowing glass dipping Polyolefin Formation high and preparation method thereof Download PDFInfo
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The present invention relates to a kind of high durable flowing glass dipping Polyolefin Formation high and preparation method thereof.In parts by mass, formula includes：1) 100 parts of polyolefin；2) 0.5 2 parts of anti-ultraviolet ageing auxiliary agent；3）0.5 2 parts of antioxidant；4）0.2 2 parts of flow improver additive；5）2 10 parts of toughener；6）15 parts of compatilizer；By above component it is pre- according to a certain percentage it is mixed after, be extruded into die head and shunted and impregnated by double/single screw extrusion machine melting mixing, be obtained high durable it is high flowing glass dipping polyolefin.The invention reside in：Hyperbranched tail end active function groups are combined with glass, enhance the Interface adhesive strength between vistanex and glass, improve mechanical property.
Description
Technical field
The present invention relates to plastic manufacturing technology field, more particularly to a kind of high durable flowing glass dipping polyolefin high is matched somebody with somebody
Side and preparation method thereof.
Background technology
In general-purpose plastics species, conventional polyolefin refers mainly to polyethylene and polypropylene.Polyethylene（Polyethylene,
Abbreviation PE）A kind of thermoplastic resin of prepared by being by vinyl monomer polymerization, industrially also includes ethene and a small amount of alpha-olefin
Copolymer.Polyethylene odorless, nontoxic, feel ceraceous, with excellent resistance to low temperature, chemical stability is good, is resistant to most of
The erosion of soda acid, is widely used in the fields such as film, hollow product, electric wire, tubing.Polypropylene
（Polypropylene, abbreviation PP）A kind of thermoplastic resin of prepared by being by propylene polymerization, also including propylene and a small amount of ethene
Copolymer including, usually translucent colorless solid, odorless is nontoxic；The highly crystallized due to compound with regular structure, therefore fusing point can
Up to 167 DEG C.Density is small, is most light general-purpose plastics；Particularly stable to water, water absorption rate is only 0.01% or so in water；It is resistance to
Hot, corrosion-resistant, product can be its outstanding advantages with moise-heat sterilization.Its intensity, rigidity, hardness heat resistance are superior to the poly- second of low pressure
Alkene, can use at 100 DEG C or so.Influenceed with good dielectric properties and high-frequency insulation and not by humidity.Due to more than it
Excellent performance, is widely used in the fields such as packaging, tubing, clothes, automobile, household electrical appliance.But it is in -35 DEG C of low temperature time-varying
It is crisp, it is not wear-resisting, easily aging.
With the improvement of living standards and energy-conservation, emission reduction, environmental protection, the enhancing of Consciousness of Sustainable Development, in automobile, family expenses
Many fields such as electrical equipment are proposed high performance, light-weighted requirement.Although such as strength of PP is higher than polyethylene, stretching
Intensity limits its application in high performance requirements field up to more than 30MPa.Make a general survey of the hair of enhancing by polymer plastics
Exhibition, is protruded the most with aramid fiber, carbon fiber, glass fiber reinforced polymer material, and performance can be matched in excellence or beauty or even be had with steel
And without too late, density but well below steel, and wherein with glass fiber high-strength, Gao Mo and cost is relatively low enjoys market
Concern and welcome.(Long Glass Fiber Reinforced Polypropylene. are referred to as long glass fiber-reinforced polypropylene
LGFPP) it is one of new varieties extremely of concern.In 20-30MPa, bending strength exists general acrylic resin tensile strength
25-50MPa, bending modulus is between 800-1500MPa, and the tensile strength of LGFPP brings up to 100-150MPa, is pure resin
3-5 times, bending strength and modulus are also original 3-5 times or so, and mechanical property is greatly improved；When being made unidirectional continuous glass-fiber
During enhancing sheet material, its tensile strength is up to 700-1000MPa, is combined into multi-layered board after-drawing intensity and also may be up to 300-
400MPa.Used as motor vehicle module carrier material, the material can not only effectively improve the rigidity of product, impact strength, anti-compacted
Become performance and dimensional stability, and the motor vehicle module product of complexity can be made.
But, on the one hand due to the application of some specific areas, it is chronically exposed under sunshine, to uvioresistant performance and heat
Oxidative aging can propose requirement higher, such as 1000h thermo-oxidative ageings after-drawing strength character retention rate need to reach at 140 DEG C
More than 80%；On the other hand, existing polypropylene material is poor to glass dipping effect, directly affects the mechanical property of product；Have
Degradation treatment is carried out to polypropylene with peroxide by technological improvement to improve its mobile performance, or addition lubrication or flowing
The micromolecule additives such as accelerator are modified to PP, PE, although improve the mobile performance of polyolefin, improve itself and glass
Dipping effect, but compromise their mechanical property simultaneously.Further, since polyolefine material viscosity regulation Shortcomings, make
When it is applied to unidirectional continuous glass-fiber enhancing sheet material, in the market crystalline p p sheet thickness can only achieve 0.2-0.3mm, polythene strip
Material thickness is main in 0.25-0.3mm, can not meet lightweight and high performance growth requirement.
The content of the invention
In view of the shortcomings of the prior art, it is poly- it is an object of the invention to provide a kind of high durable flowing glass dipping high
Alkene and preparation method thereof.
One aspect of the present invention provides a kind of high durable flowing glass dipping polyolefin high, it is characterised in that：In parts by mass,
Formula includes：
1) 100 parts of polyolefin；
2) anti-ultraviolet ageing auxiliary agent 0.5-2 parts；
3）Antioxidant 0.5-2 parts；
4）Flow improver additive 0.2-2 parts；
5）Toughener 2-10 parts；
6）Compatilizer 1-5 parts.
Preferably, described polyolefin is selected from the one kind in polyethylene, polypropylene.
Preferably, described anti-ultraviolet ageing auxiliary agent is selected from polymerized hindered amine light stabilizer HS-944, polymerized hindered
One kind in amine light stabilizer HS-950.
Preferably, described antioxidant is selected from antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant DSTP, anti-
One or more compoundings in oxygen agent P-EPQ, antioxidant PEP-36A, antioxidant 300, antioxidant PAT 218.
Preferably, described flow improver additive is selected from super-branched polymer resin HyperC100T, dissaving polymer tree
One kind in fat CYD-2136PE.
Preferably, described toughener is selected from POE POE, ethylene vinyl acetate copolymer EVA, benzene second
It is alkene-BS SBS, SIS SIS, nano silicon, super
One or more compoundings in branched resin CYD-6100 etc..
Preferably, described compatilizer is selected from graft with polyolefin as carrier, grafted monomers be maleic anhydride MAH or
GMA GMA.
The present invention has the beneficial effect that some：
1）For dipping glass vistanex and glass fibre structure feature, using dissaving polymer to its mobile performance
It is improved with compatibility, the glass fiber enhanced thermoplastic material excellent so as to reach processability；Wherein dissaving polymer is micro-
It is that matrix has fine compatibility with polyolefin to see structure, and branched end is the active function for having very good adhesion with glass
The globular molecule of group；Because this chondritic plays lubricant effect to molecular polyolefin chain, polyolefin melt is substantially increased
Mobile performance, make that when its glass fiber reinforced materials application and sheet material ultrathin, high performance can be realized；And hyperbranched tail end activity
Functional group is combined with glass, enhances the Interface adhesive strength between vistanex and glass, improves mechanical property.
2）Using high-performance polymerized hindered amine light stabilizer, with the compatibility and resistant to extraction splendid with vistanex
Property, molecular weight distribution is narrower compared with traditional hindered amine as light stabilizer, and effective nitrogen content more can be high；Again with various synergistic antioxidant
Compounded, the length or continuous glass-fiber enhancing TPO plastics having excellent weather resistance is obtained.
One aspect of the present invention provides the preparation method that high durable flowing glass high impregnates polyolefin, it is characterised in that：Including
Following steps：
By above component it is pre- according to a certain percentage it is mixed after, being extruded into die head by double/single screw extrusion machine melting mixing is carried out
Shunting and dipping, are obtained high durable flowing glass dipping polyolefin high.
Screw extruder temperature is 180-250 DEG C when preferably, with polyethylene as matrix resin；Die head temperature 220-250
℃。
Screw extruder temperature is when preferably, with polypropylene as matrix resin：200-250℃；Die head temperature 230-260
℃。
This preparation method has the beneficial effect that：
The long glass fiber reinforced polyolefin particles good mechanical performance that the preparation method is prepared, has excellent weather resistance；Prepare
Continuous glass-fiber enhancing TPO sheet material can realize ultrathin and high performance, the compound sheet material mechanical strength for obtaining is more
Height, having excellent weather resistance can meet the application of many specific areas.The PP Pipe Compound can be processed according to conventional glass impregnating equipment, be had
Important application value realistic, wide market.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
Other accompanying drawings are obtained with according to these accompanying drawings.
Fig. 1 is various embodiments of the present invention mechanical property table.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Material used, reagent etc. in following embodiments, unless otherwise specified, commercially obtain.
Polyolefin：（a）Polyethylene, refers mainly to the copolymer of HDPE, LDPE, LLDPE and ethene and a small amount of alpha-olefin, its
Melt index is more than or equal to 15g/10min；（b）Polypropylene refers mainly to propylene polymerization or propylene and a small amount of ethylene copolymer, its
Melt index is more than or equal to 25g/10min.Wherein polyolefin and combinations thereof refers mainly to PE or PP, and wherein PE can be
One or more compound systems of HDPE, LDPE, LLDPE and ethene and the copolymer of a small amount of alpha-olefin, PP can be
The single variety or compound system of isotactic polypropylene or COPP.
Specific embodiment 1
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：The kg of HDPE resin 100, uvioresistant
Line auxiliary agent HS-944 0.5 kg, antioxidant 1010 0.2kg, irgasfos 168 0.1kg, antioxidant DSTP 0.2kg, it is hyperbranched
Fluoropolymer resin Hyper C100T 0.2 kg, POE POE 2kg, polycthylene grafted Glycidyl methacrylate is sweet
Grease PE-g-GMA 1kg.
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by single screw rod unit melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, check rod is obtained long glass fiber reinforced thermoplasticity grain through supercooled water cooling granulation
Sub- LFRT, glass fiber content 50%.
Specific embodiment 2
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：：HDPE resin 80 kg, LLDPE
20kg, uvioresistant auxiliary agent HS-944 2 kg, antioxidant 1010 0.4kg, irgasfos 168 0.2kg, antioxidant DSTP
0.4kg, super-branched polymer resin Hyper C100T 2 kg, ethylene vinyl acetate copolymer EVA 5kg, it is polycthylene grafted
Maleic anhydride PE-g-MAH 3kg.
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by single screw rod unit melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, check rod is obtained long glass fiber reinforced thermoplasticity grain through supercooled water cooling granulation
Sub- LFRT, glass fiber content is controlled 50% or so.
Specific embodiment 3
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：The kg of homopolymerization PP resin 100, anti-purple
Outside line auxiliary agent HS-950 2 kg, antioxidant 1010 0.4kg, irgasfos 168 0.1kg, antioxidant PAT218 0.8kg, over-expense
The kg of fluidized polymer resin CYD-2136PE 1.2, POE POE 6kg, polypropylene grafted maleic anhydride PP-g-
MAH 5kg。
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by single screw rod unit melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, check rod is obtained long glass fiber reinforced thermoplasticity grain through supercooled water cooling granulation
Sub- LFRT, glass fiber content 50%.
Specific embodiment 4
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：The kg of homopolymerization PP resin 70, copolymerization
PP resins 30kg；Uvioresistant auxiliary agent HS-950 2 kg, antioxidant 1010 0.4kg, irgasfos 168 0.1kg, antioxidant
PAT218 1.5kg, super-branched polymer resin Hyper C100T 1.0 kg, POE POE 5kg, polypropylene
Grafted maleic anhydride PP-g-MAH 2kg.
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by twin-screw set melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, check rod is obtained long glass fiber reinforced thermoplasticity grain through supercooled water cooling granulation
Sub- LFRT, glass fiber content 50%.
Specific embodiment 5
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：HDPE resin 80 kg, LLDPE
20kg, uvioresistant auxiliary agent HS-944 2 kg, antioxidant 1010 0.4kg, irgasfos 168 0.2kg, antioxidant DSTP
0.4kg, super-branched polymer resin CYD-2136PE 2 kg, hyperbranched resin CYD-6100 5kg, polycthylene grafted methyl
Glycidyl acrylate PE-g-GMA 4kg.
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by single screw rod unit melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, in flakes after carry out compacting cooling and shaping, winding by steel rider, be obtained continuous
Fiberglass reinforced thermoplasticity band CFRT, glass fiber content is controlled in 60% or so, thickness of strip 0.22mm.
Specific embodiment 6
A kind of high durable flowing glass dipping polyolefin high, in parts by mass, formula includes：The kg of homopolymerization PP resin 100, anti-purple
Outside line auxiliary agent HS-950 2 kg, antioxidant 1010 0.4kg, irgasfos 168 0.1kg, antioxidant PAT218 0.8kg, over-expense
Fluidized polymer resin Hyper C100T 1.2 kg, POE POE 6kg, polypropylene grafted maleic anhydride PP-g-
MAH 3kg。
A kind of described high durable flowing glass high impregnates the preparation method of polyolefin, comprises the following steps：By above group
It is part pre- according to a certain percentage it is mixed after, be extruded into " clothes hanger " pattern head by twin-screw set melting mixing and shunted, finally
Glass is sufficiently impregnated into " S " pattern head, in flakes after carry out compacting cooling and shaping, winding by steel rider, be obtained continuous
Fiberglass reinforced thermoplasticity band CFRT, glass fiber content is controlled in 60% or so, thickness of strip 0.18mm；Then by its band according to
0 ° and 90 ° intersection laying of machine direction, the sheet material that thickness is 3mm or so is obtained by laminating apparatus.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of high durable flowing glass high impregnates polyolefin, it is characterised in that：In parts by mass, formula includes：
1) 100 parts of polyolefin；
2) anti-ultraviolet ageing auxiliary agent 0.5-2 parts；
3）Antioxidant 0.5-2 parts；
4）Flow improver additive 0.2-2 parts；
5）Toughener 2-10 parts；
6）Compatilizer 1-5 parts.
2. high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described polyolefin choosing
One kind from polyethylene, polypropylene.
3. high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described uvioresistant is old
Change the one kind during auxiliary agent is selected from polymerized hindered amine light stabilizer HS-944, polymerized hindered amine light stabilizer HS-950.
4. high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described antioxidant choosing
From antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant DSTP, antioxidant P-EPQ, antioxidant PEP-36A, antioxidant
300th, one or more compoundings in antioxidant PAT 218.
5. high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described flowing promotes
Agent is selected from the one kind in super-branched polymer resin Hyper C100T, super-branched polymer resin CYD-2136PE.
6. a kind of high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described toughness reinforcing
Agent is selected from POE POE, ethylene vinyl acetate copolymer EVA, styrene-butadiene-styrene
In SBS, SIS SIS, nano silicon, hyperbranched resin CYD-6100 etc.
One or more compoundings.
7. a kind of high durable according to claim 1 flowing glass high impregnates polyolefin, it is characterised in that：Described is compatible
Agent is selected from the graft with polyolefin as carrier, and grafted monomers are maleic anhydride MAH or GMA GMA.
8. a kind of high durable according to claim 1 to 6 any one flowing glass high impregnates the preparation method of polyolefin,
It is characterized in that：Comprise the following steps：
By above component it is pre- according to a certain percentage it is mixed after, being extruded into die head by double/single screw extrusion machine melting mixing is carried out
Shunting and dipping, are obtained high durable flowing glass dipping polyolefin high.
9. high durable according to claim 7 flowing glass high impregnates the preparation method of polyolefin, it is characterised in that：With poly-
Screw extruder temperature is 180-250 DEG C when ethene is matrix resin；220-250 DEG C of die head temperature.
10. high durable according to claim 7 flowing glass high impregnates the preparation method of polyolefin, it is characterised in that：With
Screw extruder temperature is when polypropylene is matrix resin：200-250℃；230-260 DEG C of die head temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710236768.2A CN106916358A (en) | 2017-04-12 | 2017-04-12 | A kind of high durable flowing glass dipping Polyolefin Formation high and preparation method thereof |
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| CN108276682A (en) * | 2017-12-26 | 2018-07-13 | 上海普利特复合材料股份有限公司 | A kind of high fluidity polypropylene composite material with high strength and toughness and preparation method thereof |
| CN111087691A (en) * | 2019-12-23 | 2020-05-01 | 上海普利特复合材料股份有限公司 | High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof |
| CN111849064A (en) * | 2019-04-25 | 2020-10-30 | 振石集团华美新材料有限公司 | Continuous glass fiber reinforced polypropylene prepreg tape and preparation method thereof |
| CN112745576A (en) * | 2020-12-30 | 2021-05-04 | 上海聚威新材料股份有限公司 | High-heat-resistance and high-weather-resistance long glass fiber reinforced polypropylene material and preparation method thereof |
| CN113136061A (en) * | 2021-03-26 | 2021-07-20 | 广东聚石化学股份有限公司 | Flame-retardant polyethylene material and preparation method and application thereof |
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| CN108276682A (en) * | 2017-12-26 | 2018-07-13 | 上海普利特复合材料股份有限公司 | A kind of high fluidity polypropylene composite material with high strength and toughness and preparation method thereof |
| CN111849064A (en) * | 2019-04-25 | 2020-10-30 | 振石集团华美新材料有限公司 | Continuous glass fiber reinforced polypropylene prepreg tape and preparation method thereof |
| CN111087691A (en) * | 2019-12-23 | 2020-05-01 | 上海普利特复合材料股份有限公司 | High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof |
| CN112745576A (en) * | 2020-12-30 | 2021-05-04 | 上海聚威新材料股份有限公司 | High-heat-resistance and high-weather-resistance long glass fiber reinforced polypropylene material and preparation method thereof |
| CN113136061A (en) * | 2021-03-26 | 2021-07-20 | 广东聚石化学股份有限公司 | Flame-retardant polyethylene material and preparation method and application thereof |
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