CN106279989B - Glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application - Google Patents
Glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application Download PDFInfo
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- CN106279989B CN106279989B CN201610694926.4A CN201610694926A CN106279989B CN 106279989 B CN106279989 B CN 106279989B CN 201610694926 A CN201610694926 A CN 201610694926A CN 106279989 B CN106279989 B CN 106279989B
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- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/004—Additives being defined by their length
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The present invention provides a kind of glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application, the composition includes super high molecular weight ultra-fine grain diameter acrylic polymers and glass fibre；The viscosity average molecular weigh (Mv) of the super high molecular weight ultra-fine grain diameter acrylic polymers is greater than 1 × 106；The super high molecular weight ultra-fine grain diameter acrylic polymers is spheric granules, and average grain diameter is 10 μm -200 μm, and standard deviation is 2 μm -15 μm, and heap density is 0.1g/mL-0.4g/mL.The sheet material or pipe have excellent resistance to low temperature, shock resistance and creep resistance.In addition, the mechanical performance of the sheet material or pipe is also very excellent due to the humidification of glass fibre.Therefore, sheet material of the invention is especially suitable for numerous areas such as automobile, electronic devices, and the pipe is particularly suitable for fields such as water supply and drainage, oil drillings.
Description
Technical field
The present invention relates to a kind of propylene compositions and its applications, and in particular to a kind of glass fiber reinforcement acrylic polymers group
Close object, sheet material prepared therefrom or pipe and its application.
Background technique
Polypropylene is one of maximum general-purpose plastics kind of current dosage, has more balanced comprehensive performance, thus
It is largely used in fields such as automobile, electric appliance, building materials.The highly crystallized due to compound with regular structure, polyacrylic fusing point can be high
Up to 167 DEG C, heat-resisting, excellent anti-corrosion performance, but it is low temperature resistant simultaneously, impact resistance is poor, more easy to aging.
Glass fiber reinforced polypropylene (GFPP) is because it has improved rigidity, impact strength, creep-resistant property, low sticks up
The advantages that bent, anti-dynamic fatigue and dimensional stability, the concern by more and more researchers in recent years, although glass fibre
Reinforced polypropylene can improve its resistance to low temperature, but there are still glass fibre and polyacrylic poor compatibility, impact resistance and
The problems such as creep-resistant property is low has novel glass fiber reinforced polypropylene composite material to be developed.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of novel glass fiber reinforcement propylene polymerization
Compositions, the resistance to low temperature of sheet material or pipe prepared therefrom is excellent, every mechanical property (especially shock resistance and anti-
Croop property) and thermal property it is very excellent.
In order to solve the above technical problems, the present invention provides a kind of glass fiber reinforcement prolylene polymer composition, packet
Include super high molecular weight ultra-fine grain diameter acrylic polymers and glass fibre；
The viscosity average molecular weigh (Mv) of the super high molecular weight ultra-fine grain diameter acrylic polymers is greater than 1 × 106；The superelevation point
Son amount ultra-fine grain diameter acrylic polymers is spheric granules, and average grain diameter is 10 μm -200 μm, and standard deviation is 2 μm -15 μm, heap density
For 0.1g/mL-0.4g/mL.
Preferably, the particle diameter distribution of the super high molecular weight ultra-fine grain diameter acrylic polymers is similar to normal distribution.
According to the present invention, the super high molecular weight ultra-fine grain diameter acrylic polymers be Noblen or propylene copolymer,
Comonomer in propylene copolymer is C2-20Alpha-olefin, such as ethylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1-
One of octene, 1- nonene, 1- decene, 1- hendecene or 1- laurylene are a variety of.Preferably, the comonomer is ethylene
One or both of with 1- butylene.The molar content of the comonomer is 0-10mol%, preferably 0-5mol%.
According to the present invention, the viscosity average molecular weigh (Mv) of the super high molecular weight ultra-fine grain diameter acrylic polymers is more than or equal to
1.5×106, it is therefore preferable to 1.5 × 106~4.0 × 106；The molecular weight of the super high molecular weight ultra-fine grain diameter acrylic polymers point
Cloth Mw/Mn is 2~15, preferably 3~10, also preferably 4~8.
According to the present invention, the average grain diameter of the super high molecular weight ultra-fine grain diameter acrylic polymers is preferably 20 μm of -180 μ
M, more preferably 30 μm -150 μm, also preferably 40-120 μm；The standard deviation is preferably 5 μm -15 μm, and more preferably 6 μm -12
μm, also preferably 8 μm -10 μm；The heap density of the super high molecular weight ultra-fine grain diameter acrylic polymers is preferably 0.15g/mL-
0.35g/mL, also preferably 0.2g/mL-0.3g/mL.
According to the present invention, the glass fibre is the glass fibre through coupling agent treatment.The coupling agent is, for example, silane
Coupling agent (such as gamma-aminopropyl-triethoxy-silane KH550, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane KH560,
γ-methacryloxypropyl trimethoxy silane KH570, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane
KH792, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane DL602, vinyltrimethoxysilane A-171, second
Alkenyl triethoxysilane A-151 etc.), titanate coupling agent (such as isopropyl tri(dioctylpyrophosphato)titanate, two (two
Octyl phosphinylidyne oxygroup) metatitanic acid second diester, diisostearoyl ethylene titanate) or one of aluminate coupling agent or a variety of.
Preferably, the coupling agent is selected from silane coupling agent, particularly preferred gamma-aminopropyl-triethoxy-silane KH550, vinyl front three
Oxysilane A-171, vinyltriethoxysilane A-151 etc..In addition, in order to enable glass fibre is more preferably dispersed in the idol
Join in agent, diluent can be added in the system of the glass fibre and coupling agent, the diluent is for example selected from white oil or liquid
Body paraffin.The weight ratio of the diluent and coupling agent for example (1~10): 1, preferably (3~6): 1.
According to the present invention, the length of the glass fibre be 0.5mm-10mm, for example, 1mm-3mm or 3mm-5mm, or
5mm-7mm etc..
According to the present invention, in the composition each component weight percentage are as follows: super high molecular weight ultra-fine grain diameter propylene
Polymer 10-95wt%, glass fibre 5-90wt%.Preferably, the content of the glass fibre is 10-80wt%, more preferably
For 40-70wt%.
The present invention also provides a kind of sheet material or pipes, are prepared by above-mentioned composition.
The present invention also provides a kind of preparation methods of above sheet comprising following steps: the super high molecular weight is surpassed
Fine grain acrylic polymers and the glass fibre are uniformly mixed in high-speed mixer, are added in extruder, are passed through sheet material mould
Tool squeezes out, and through cooling, stretches, sheet material of the invention is made.
The present invention also provides a kind of preparation methods of above-mentioned pipe comprising following steps: the super high molecular weight is ultra-fine
Partial size acrylic polymers and the glass fibre are uniformly mixed in high-speed mixer, are added in extruder, are passed through pipe mold
It squeezes out, through cooling, stretches, pipe of the invention is made.
Preferably, the wall thickness of the pipe is between 0.1mm-10mm, between preferably 0.5mm-5mm.
Invention further provides the purposes of above sheet, can be used for the numerous areas such as automobile, electronic device.
The present invention still further provides the purposes of above-mentioned pipe, the fields such as water supply draining, oil drilling, such as makees
For water supply and drainage pipe or mining wear resistance pipe etc..
Beneficial effects of the present invention:
The present invention proposes a kind of glass fiber reinforcement prolylene polymer composition, the sheet material that prepared by the composition or
Pipe has excellent resistance to low temperature (can such as be used for a long time at subzero 30 DEG C to subzero 175 DEG C), shock resistance (such as
Simply supported beam notch impact strength (7.5J) is higher than 10.0KJ/m2) and creep resistance (such as creep is less than or equal to 2.5%).In addition,
Due to the humidification of glass fibre, the mechanical performance of the sheet material or pipe (such as bending strength, bending modulus, tensile strength and
Heat distortion temperature etc.) it is also very excellent.Therefore, sheet material of the invention is especially suitable for the numerous areas such as automobile, electronic device, institute
Pipe is stated particularly suitable for fields such as water supply and drainage, oil drillings.
Specific embodiment
[preparation method of catalyst]
The catalyst used in the preparation method of super high molecular weight ultra-fine grain diameter acrylic polymers of the invention can use
The preparation of method disclosed in the application for a patent for invention (application number 201510271254.1) that applicant has been filed on, full text introduce this
As reference in application.
Specifically, above-mentioned catalyst is prepared by method comprising the following steps:
(a) magnesium halide, alcohol compound, auxiliary agent, the internal electron donor of part and solvent are mixed, mixture I is made；
(b) above-mentioned mixture I is added in the reactor, is preheating to -30 DEG C~30 DEG C, titanium compound is added dropwise；Alternatively,
Titanium compound is added in reactor, is preheating to -30 DEG C~30 DEG C, above-mentioned mixture I is added dropwise；
(c) after being added dropwise to complete, reaction system was warming up to 90 DEG C~130 DEG C by 30 minutes~3 hours, was added in remaining
The reaction was continued for electron donor；
(d) remaining titanium compound is added in the liquid for filtering out reaction system, and the reaction was continued；
(e) after the reaction was completed, post-processing obtains the catalyst.
In the present invention, the step (b) is replaced by following step (b '):
(b ') configuration includes the mixtures II of nanoparticle, dispersing agent and solvent；
Above-mentioned mixture I and mixtures II are added in the reactor and obtains the mixture of the two, is preheating to -30 DEG C~30
DEG C, titanium compound is added dropwise；Alternatively,
Titanium compound is added in the reactor, is preheating to -30 DEG C~30 DEG C, above-mentioned mixture I and mixtures II is added dropwise
Mixture.
In the present invention, the mixture I is preferably prepared as follows: by magnesium halide and alcohol compound organic
It is mixed in solvent, after heating up and keeping the temperature, auxiliary agent and partial internal electron donor is added, obtain stablizing after certain temperature reaction equal
One mixture I.The alcohol compound is selected from C1-C15Fatty alcohols compound, C3-C15Cycloalkanes alcohol compound and C6-
C15One or more of aromatic alcohol compound, preferably methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, 1,3- third
One in glycol, butanol, isobutanol, hexanol, enanthol, n-octyl alcohol, isooctanol, nonyl alcohol, decyl alcohol, sorbierite, cyclohexanol and benzylalcohol
Kind is several, more preferably ethyl alcohol, butanol, hexanol and isooctanol.The internal electron donor is monoesters, diester, monoether, two ethers
At least one of compound is more preferably selected from diester or diether.The solvent is selected from linear paraffin, the 5-20 of 5-20 carbon
At least one of the branched paraffin of a carbon, the aromatic hydrocarbon of 6-20 carbon or their halogenated hydrocarbons, preferably toluene, chlorobenzene, dichloro
At least one of benzene or decane.In the present invention, magnesium halide can directly obtain urging for submicron order polyolefin particles in preparation
Have the function of carrier in agent, be one of the composition of traditional Ziegler Natta, the catalyst of preparation can be made to have and closed
Suitable shape, size and mechanical strength, meanwhile, carrier can make active component dispersion on the surface of the carrier, and acquisition is higher to compare table
Area improves the catalytic efficiency of unit mass active component.In addition, the effect of the alcohol compound is carrier i.e. halogenation
Magnesium dissolution.In the preparation process of mixture I, the temperature for obtaining mixed solution is preferably 110 DEG C -130 DEG C, more preferably
130 DEG C, the soaking time is preferably 1-3 hours, and more preferably 2-3 hours, the reaction time being added after auxiliary agent etc. was
0.5-2 hours, more preferably 1 hour.Therefore, magnesium halide is dissolved by alcohol compound at high temperature, has obtained mixture I.
In the present invention, the mixture II is preferably prepared as follows: nanoparticle, dispersing agent and solvent are added
Enter into reaction vessel, is ultrasonically treated, obtains uniform mixture II.The nanoparticle be preferably nano silica,
At least one of nano-titanium dioxide, nano zirconium dioxide, nano-nickel oxide, nanometer magnesium chloride or nano carbon microsphere, more preferably
For nano silica, nano-titanium dioxide.The granularity of nanoparticle is preferably 1-80nm, more preferably 10-50nm.Preferably
The addition quality of nanoparticle is 0%-200%, more preferably 0%-20% relative to the addition quality of magnesium halide.Ultrasonic treatment
Time be preferably 2 hours.Nanoparticle is introduced as crystal seed in the present invention, in order to accelerate the molding and drop of carrier
The partial size of low catalyst particle；Dispersing agent and solvent, including ultrasonic treatment are provided to help nanoparticle dispersion, promote in this way
Each nano particle can play the effect of crystal seed.
In the present invention, in the mixtures II of the step (b '), the nanoparticle is selected from nano silica, nanometer two
At least one of titanium oxide, nano zirconium dioxide, nano-nickel oxide, nanometer magnesium chloride or nano carbon microsphere.
Preferably, the granularity of the nanoparticle is 1-80 nanometers, preferably 2-60 nanometers, 3-50 nanometers more preferable.
The addition quality of the nanoparticle relative to magnesium halide addition quality be greater than 0% to less than be equal to 200%,
Preferably, the range of the nanoparticle additional amount is greater than 0% to less than equal to 20%.
In the present invention, in the mixtures II of the step (b '), the solvent is selected from linear paraffin, the 5-20 of 5-20 carbon
At least one of the branched paraffin of a carbon, the aromatic hydrocarbon of 6-20 carbon or their halogenated hydrocarbons.
The dispersing agent is selected from the mixture of titanium tetrachloride, silicon tetrachloride or both.
In step (a), described be blended under heating stirring is carried out, and obtains the transparent mixture I of stable homogeneous.
In step (b '), ultrasonic disperse processing is carried out when configuration.
In step (b) or (b '), it is added dropwise to be slowly added dropwise.
In step (b) or (b '), preferred preheating temperature of reacting is -20 DEG C~30 DEG C, more preferably -20 DEG C~20 DEG C.
The reaction time of step (c) is 1-5 hours, preferably 2-3 hours.
Step (d) time that the reaction was continued is 1-5 hours, preferably 2-3 hours.
Post-processing in step (e), which can be, cleans products therefrom with hexane, then dries；Wherein, cleaning
Number can be 1-10 times, and preferably 3-6 times.
In step (a), the magnesium halide is selected from least one of magnesium chloride, magnesium bromide or magnesium iodide.
In step (a), the auxiliary agent can be titanate ester compound.
In step (b) or (b '), the general formula of the titanium compound is shown in formula I:
Ti(R)nX(4-n)
Formulas I
Wherein, R is the branched-chain or straight-chain alkyl of C1-C12, and X is halogen, n 0,1,2 or 3.
In step (d), it is preferred that reaction system was warming up to 90 DEG C~130 DEG C by 40 minutes~3 hours, more preferably anti-
System is answered to be warming up to 100 DEG C~120 DEG C by 40 minutes~2 hours.
From above scheme as can be seen that the preparation method simple process of Ziegler-Natta catalyst according to the present invention,
It is easy to industrialized production.Also, average grain diameter can be made in propylene polymerization for Ziegler-Natta catalyst prepared by the present invention
It is 10 μm -200 μm, sphericity is higher, and particle diameter distribution is relatively narrow, the propylene polymerization composition granule of heap density low (for 0.1-0.4g/mL).
By the study found that the acrylic polymers that catalyst prepared by the present invention is obtained for propylene polymerization particle compared to other,
Partial size has 20-30 times of reduction, and particle diameter distribution obviously narrows and heap density can be down to 0.1g/mL.
[super high molecular weight ultra-fine grain diameter acrylic polymers and preparation method thereof]
As described above, a kind of super high molecular weight ultra-fine grain diameter acrylic polymers is used in the present composition, described third
The viscosity average molecular weigh (Mv) of alkene polymer is greater than 1 × 106, the acrylic polymers be spheric granules, average grain diameter be 10 μm-
200 μm, standard deviation is 2 μm -15 μm, and heap density is 0.1g/mL-0.4g/mL.Preferably, the partial size of the acrylic polymers point
Cloth is similar to normal distribution.The average grain diameter is preferably 20 μm -180 μm, more preferably 30 μm -150 μm, also preferably 40-
120μm.The standard deviation is preferably 5 μm -15 μm, more preferably 6 μm -12 μm, also preferably 8 μm -10 μm.The heap density is excellent
It is selected as 0.15g/mL-0.35g/mL, also preferably 0.2g/mL-0.3g/mL.The supra polymer for having the partial size and heap density
Acrylic polymers is measured, especially suitable for graft modification, on the one hand greatly extends the modification space of acrylic polymers；Another party
The processing performance in face, the polymer significantly improves, the preparation suitable for larger range of product；In this way, just effectively extending
The application field of the polymer.
Meanwhile acrylic polymers of the invention is also equipped with following excellent properties: firstly, abrasion resistance properties are very brilliant, than
The also high several times of abrasion resistance index of the general metals such as carbon steel and copper；Secondly as molecular weight superelevation, strand overlength, so that material
Impact strength it is high；Again, the ability resistant to chemical etching of the acrylic polymers is better than general polyolefin；Finally, the material makes
With wider range, it is able to maintain good toughness and intensity at lower or higher temperatures.
As described above, the present invention provides the preparation method of above-mentioned super high molecular weight ultra-fine grain diameter acrylic polymers, packet
Include following steps:
Under the action of catalyst, propylene or propylene and comonomer carry out polymerization reaction, wherein the temperature of polymerization reaction is
30-105 DEG C, the volume fraction of the propylene is more than or equal to 98%；
The catalyst is prepared by the preparation method of above-mentioned catalyst.
The present invention passes through the study found that simply control the preparation method of the catalyst, can realize institute very well really
The control of the partial size of acrylic polymers is stated, but the molecular weight of the acrylic polymers prepared is not high, in order to realize control partial size
The molecular weight of the polymer is improved simultaneously, inventor has carried out many trials, it has been investigated that, control the temperature of polymerization reaction
The purity of degree and monomer is a kind of simple and effective method, and will not influence effective control of the polymer partial size,
Even help to prepare the polymer of narrower particle size range and more low bulk density range.
By the way that the study found that the temperature control of the polymerization reaction is at 30-105 DEG C, the volume fraction of propylene is controlled big
In equal to 98%, so that it may prepare the acrylic polymers of super high molecular weight while realizing size controlling.It is further preferred that institute
The temperature for stating polymerization reaction is 40~80 DEG C.It is further preferred that the volume fraction of the propylene is more than or equal to 99%；It is also more excellent
Selection of land is more than or equal to 99.8%；It is more preferred still that being more than or equal to 99.9%.For copolymerization, an oxygen in comonomer is controlled
Change carbon content and be less than 10ppm less than 15ppm, conjugated diene hydrocarbon content less than 5ppm, carbon dioxide, is also beneficial to the object of the invention
Realization.
In the present invention, propylene volume fraction is determined by standard GB/T3392.Propylene volume fraction is the characterization propylene
One important indicator of the purity of monomer.
In an embodiment of the invention, a kind of preparation side of super high molecular weight ultra-fine grain diameter acrylic polymers is provided
Method comprising following steps:
Under the action of catalyst, propylene or propylene and comonomer carry out polymerization reaction, wherein the temperature of polymerization reaction is
30-105 DEG C, the volume fraction of the propylene is more than or equal to 98%；
The catalyst is prepared by method comprising the following steps:
(a) magnesium halide, alcohol compound, auxiliary agent, the internal electron donor of part and solvent are mixed, mixture I is made；
(b) above-mentioned mixture I is added in the reactor, is preheating to -30 DEG C~30 DEG C, titanium compound is added dropwise；Alternatively,
Titanium compound is added in reactor, is preheating to -30 DEG C~30 DEG C, above-mentioned mixture I is added dropwise；
(c) after being added dropwise to complete, reaction system was warming up to 90 DEG C~130 DEG C by 30 minutes~3 hours, was added in remaining
The reaction was continued for electron donor；
(d) remaining titanium compound is added in the liquid for filtering out reaction system, and the reaction was continued；
(e) after the reaction was completed, post-processing obtains the catalyst；
Wherein the viscosity average molecular weigh (Mv) of acrylic polymers obtained is greater than 1 × 106；The acrylic polymers is spherical
Grain, average grain diameter are 10 μm -200 μm, and standard deviation is 2 μm -15 μm, and heap density is 0.1g/mL-0.4g/mL.
In the present invention, the particle diameter distribution of the acrylic polymers is similar to normal distribution.
In the present invention, the comonomer is C2-20Alpha-olefin, such as ethylene, 1- butylene, 1- amylene, 1- hexene, 1-
One of heptene, 1- octene, 1- nonene, 1- decene, 1- hendecene or 1- laurylene are a variety of.Preferably, the copolymerization is single
Body is one or both of ethylene and 1- butylene.The molar content of the comonomer is 0-10mol%, preferably 0-
5mol%.
In the present invention, the temperature of the polymerization reaction is preferably 40~80 DEG C.
In the present invention, the volume fraction of the propylene is also more excellent more than or equal to 99%, more preferably greater than or equal to 99.8%
Selection of land is more than or equal to 99.9%.
In the present invention, in the comonomer (such as ethylene or 1- butylene), carbon monoxide content is less than 5ppm, carbon dioxide
Less than 15ppm, conjugated diene hydrocarbon content is less than 10ppm.
[parametric measurement]
Creep resistance is measured using the method for chinese national standard GB11546-89, ISO899-1981.
Shock resistance is measured using GB/T1043.1-2008.
Bending strength and bending modulus, are measured using GB/T9341-2008.
Tensile strength is measured using GB/T1040-2006.
Heat distortion temperature is measured using GB/T1634.2-2004.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through different specific embodiment parties
Formula is embodied or practiced, and the various details in this specification can also be based on the application of different aspect, without departing from this hair
Various modifications or alterations are carried out under bright spirit.
1 Noblen of preparation example and its preparation
In the reactor being sufficiently displaced from by high pure nitrogen, anhydrous magnesium chloride 4.94g, isooctanol 18.9g are sequentially added,
Decane 30ml is warming up to 130 DEG C under stirring, and maintains 2 hours, and 2.65g butyl titanate and 2.05g O-phthalic is then added
Sour diisobutyl ester reacts 1 hour again at 130 DEG C, is finally cooled to room temperature, forms homogeneous transparent solution, as mixture I.
200ml titanium tetrachloride is added into reaction kettle to stir and be preheated to 0 DEG C, mixture I was added drop-wise to four in 2 hours or so
In titanium chloride.It is added dropwise, starts to warm up, 110 DEG C are warming up in 2 hours.Two isobutyl of internal electron donor phthalic acid is added
Ester 1.23g.After reacting 2 hours at this temperature, reaction liquid is removed, 200ml titanium tetrachloride is added again, is reacted 2 hours.Most
It moves back except reaction liquid, 60 DEG C of hexane of remaining solid matter is rinsed 10 times, catalyst is drying to obtain.
The bulk polymerization of propylene:
Under high pure nitrogen protection, deoxygenation is dried to 5L autoclave, the above-mentioned catalyst and three of 20mg is added
Then propylene 1200g is added, wherein the volume fraction of propylene is in aluminium ethide 12ml and 3ml external electron donor Donor-P
99.9%, polymerization reaction starts, system temperature be maintained 45 DEG C, the reaction time be 60 minutes, propylene homo of the invention is made
Object.
2 propylene-ethylene copolymers of preparation example and its preparation
The preparation method of catalyst is the same as preparation example 1.
Propylene-ethylene copolymerization:
Under high pure nitrogen protection, deoxygenation is dried to 5L autoclave, the above-mentioned catalyst and three of 20mg is added
Then aluminium ethide 12ml and 3ml external electron donor Donor-P is added propylene 1200g, is passed through ethylene 40g, wherein the body of propylene
Fraction is 99.9%, and carbon monoxide content is less than 15ppm and conjugated diene less than 5ppm, carbon dioxide in ethylene gas
Hydrocarbon content is less than 10ppm, and polymerization reaction starts, system temperature be maintained 75 DEG C, the reaction time be 60 minutes, be made of the invention
Propylene-ethylene copolymers.
3 Noblen of preparation example and its preparation
The preparation method of catalyst is the same as preparation example 1.
The bulk polymerization of propylene:
Under high pure nitrogen protection, deoxygenation is dried to 5L autoclave, the above-mentioned catalyst and three of 20mg is added
Then propylene 1200g is added, wherein the volume fraction of propylene is in aluminium ethide 12ml and 3ml external electron donor Donor-P
99.9%, polymerization reaction starts, system temperature be maintained 55 DEG C, the reaction time be 60 minutes, propylene homo of the invention is made
Object.
4 Noblen of preparation example and its preparation
The preparation method of catalyst is the same as preparation example 1.
The bulk polymerization of propylene:
Under high pure nitrogen protection, deoxygenation is dried to 5L autoclave, the above-mentioned catalyst and three of 20mg is added
Then propylene 1200g is added, wherein the volume fraction of propylene is in aluminium ethide 12ml and 3ml external electron donor Donor-P
99.9%, polymerization reaction starts, system temperature be maintained 65 DEG C, the reaction time be 60 minutes, propylene homo of the invention is made
Object.
The property of the acrylic polymers of 1 preparation example 1-4 of table
Preparation example 5
In batch mixer, glass fibre and coupling agent is added, stirs 30min；Diluent is added, 30min is stirred；It obtains
Treated glass fibre of the invention.Wherein, coupling agent is gamma-aminopropyl-triethoxy-silane KH550；The length of glass fibre
Degree is 3-5mm；Diluent is white oil.The weight ratio of diluent and coupling agent is 3:1；The dosage of coupling agent, relative to 100 weight
Part glass fibre is 2 parts by weight.
Preparation example 6
In batch mixer, glass fibre and coupling agent is added, stirs 30min；Diluent is added, 30min is stirred；It obtains
Treated glass fibre of the invention.Wherein, coupling agent is vinyltrimethoxysilane A-171；The length of glass fibre
For 3-5mm；Diluent is white oil.The weight ratio of diluent and coupling agent is 4:1；The dosage of coupling agent, relative to 100 parts by weight
Glass fibre is 1 parts by weight.
Preparation example 7
In batch mixer, glass fibre and coupling agent is added, stirs 30min；Diluent is added, 30min is stirred；It obtains
Treated glass fibre of the invention.Wherein, coupling agent is vinyltriethoxysilane A-151；The length of glass fibre
For 3-5mm；Diluent is atoleine.The weight ratio of diluent and coupling agent is 6:1；The dosage of coupling agent, relative to 100 weights
Part glass fibre is measured, is 3 parts by weight.
Embodiment 1-12 glass fiber reinforcement prolylene polymer composition
The composition and content of the composition of 1-12 of the embodiment of the present invention are listed in Table 2 below.
Table 2
Embodiment 13-24
The composition that embodiment 1-12 is respectively adopted prepares sheet material.
By taking the composition of embodiment 1a as an example, by the glass fibre 4Kg of the Noblen 6kg of preparation example 1 and preparation example 5
It is uniformly mixed by high-speed mixer, extruder is added, squeezed out by a slot die, through cooling, stretched, the present invention is made
Sheet material.Wherein, the processing temperature of the extruder is 180~240 DEG C.
The performance test results of the sheet material of embodiment 13-24 preparation are shown in Table 3.
Table 3
Table 3 (continuous 1)
Table 3 (continuous 2)
Table 3 (continuous 3)
Embodiment 25-36
The composition preparation pipe of embodiment 1-12 is respectively adopted.
By taking the composition of embodiment 1a as an example, by the glass fibre 4Kg of the Noblen 6kg of preparation example 1 and preparation example 5
It is uniformly mixed by high-speed mixer, extruder is added, squeezed out by a tubing die head, through cooling, stretched, the present invention is made
Pipe.Wherein, the processing temperature of the extruder is 180~240 DEG C.The wall thickness of the pipe is between 0.5mm-5mm.
The performance test results and the similar performance of corresponding sheet material of the pipe of embodiment 25-36 preparation.
Claims (36)
1. a kind of glass fiber reinforcement prolylene polymer composition, which is characterized in that the composition includes that super high molecular weight is super
Fine grain acrylic polymers and glass fibre；
The viscosity average molecular weigh (Mv) of the super high molecular weight ultra-fine grain diameter acrylic polymers is greater than 1 × 106；The super high molecular weight
Ultra-fine grain diameter acrylic polymers is spheric granules, and average grain diameter is 10 μm -200 μm, and standard deviation is 2 μm -15 μm, and heap density is
0.1g/mL-0.4g/mL；The particle diameter distribution of the super high molecular weight ultra-fine grain diameter acrylic polymers is similar to normal distribution；
Wherein, the super high molecular weight ultra-fine grain diameter acrylic polymers is prepared using method comprising the following steps:
Under the action of catalyst, propylene or propylene and comonomer carry out polymerization reaction, wherein the temperature of polymerization reaction is 30-
105 DEG C, the volume fraction of the propylene is more than or equal to 99%；
Wherein, the preparation method that the catalyst passes through the catalyst included the following steps is prepared:
(a) magnesium halide and alcohol compound are mixed in organic solvent, after heating up and keeping the temperature, auxiliary agent is added and partial interior gives
Electron obtains mixture I after certain temperature reaction；
(b) above-mentioned mixture I is added in the reactor, is preheating to -30 DEG C~30 DEG C, titanium compound is added dropwise；Alternatively, reacting
Titanium compound is added in device, is preheating to -30 DEG C~30 DEG C, above-mentioned mixture I is added dropwise；
(c) after being added dropwise to complete, reaction system was warming up to 90 DEG C~130 DEG C by 30 minutes~3 hours, was added in remaining to electricity
The reaction was continued for daughter；
(d) liquid of reaction system is filtered out, titanium compound is added, the reaction was continued；
(e) after the reaction was completed, post-processing obtains the catalyst；
Alternatively, the preparation method that the catalyst passes through the catalyst included the following steps is prepared:
(a) magnesium halide and alcohol compound are mixed in organic solvent, after heating up and keeping the temperature, auxiliary agent is added and partial interior gives
Electron obtains mixture I after certain temperature reaction；
(b ') configuration includes the mixtures II of nanoparticle, dispersing agent and solvent；
Above-mentioned mixture I and mixtures II are added in the reactor and obtains the mixture of the two, is preheating to -30 DEG C~30 DEG C,
Titanium compound is added dropwise；Alternatively,
Titanium compound is added in the reactor, is preheating to -30 DEG C~30 DEG C, the mixed of above-mentioned mixture I and mixtures II is added dropwise
Close object；
(c) after being added dropwise to complete, reaction system was warming up to 90 DEG C~130 DEG C by 30 minutes~3 hours, was added in remaining to electricity
The reaction was continued for daughter；
(d) liquid of reaction system is filtered out, titanium compound is added, the reaction was continued；
(e) after the reaction was completed, post-processing obtains the catalyst.
2. composition according to claim 1, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers is
Noblen or propylene copolymer, the comonomer in propylene copolymer are ethylene, 1- butylene, 1- amylene, 1- hexene, 1- heptan
One of alkene, 1- octene, 1- nonene, 1- decene, 1- hendecene or 1- laurylene are a variety of.
3. composition according to claim 2, which is characterized in that the comonomer is one of ethylene and 1- butylene
Or two kinds.
4. composition according to claim 2, which is characterized in that the molar content of the comonomer is 0-
10mol%.
5. composition according to claim 1, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Viscosity average molecular weigh (Mv) is more than or equal to 1.5 × 106；The molecular weight distribution of the super high molecular weight ultra-fine grain diameter acrylic polymers
Mw/Mn is 2~15.
6. composition according to claim 5, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Viscosity average molecular weigh (Mv) is 1.5 × 106~4.0 × 106。
7. composition according to claim 5, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Molecular weight distribution mw/mn is 3~10.
8. composition according to claim 7, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Molecular weight distribution mw/mn is 4~8.
9. composition according to claim 1, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Average grain diameter is 20 μm -180 μm.
10. composition according to claim 9, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Average grain diameter be 30 μm -150 μm.
11. composition according to claim 10, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Average grain diameter be 40-120 μm.
12. composition according to claim 1, which is characterized in that the standard deviation is 5 μm -15 μm.
13. composition according to claim 12, which is characterized in that the standard deviation is 6 μm -12 μm.
14. composition according to claim 13, which is characterized in that the standard deviation is 8 μm -10 μm.
15. composition according to claim 1, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Heap density be 0.15g/mL-0.35g/mL.
16. composition according to claim 15, which is characterized in that the super high molecular weight ultra-fine grain diameter acrylic polymers
Heap density be 0.2g/mL-0.3g/mL.
17. composition according to claim 1, which is characterized in that the glass fibre is the glass through coupling agent treatment
Fiber.
18. composition according to claim 17, which is characterized in that the coupling agent is silane coupling agent, titanate esters idol
Join one of agent or aluminate coupling agent or a variety of.
19. composition according to claim 18, which is characterized in that the silane coupling agent is selected from three second of γ-aminopropyl
Oxysilane KH550, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane KH560, γ-methacryloxypropyl three
Methoxy silane KH570, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792, N- (β-aminoethyl)-γ-ammonia third
One in ylmethyl dimethoxysilane DL602, vinyltrimethoxysilane A-171, vinyltriethoxysilane A-151
Kind is a variety of；The titanate coupling agent is selected from isopropyl tri(dioctylpyrophosphato)titanate, two (dioctyl phosphinylidyne oxygen
Base) metatitanic acid second diester, diisostearoyl ethylene titanate) one of or it is a variety of.
20. composition according to claim 17, which is characterized in that add in the system of the glass fibre and coupling agent
Enter diluent, the diluent is selected from white oil or atoleine.
21. composition according to claim 20, which is characterized in that the weight ratio of the diluent and coupling agent be (1~
10):1。
22. composition according to claim 21, which is characterized in that the weight ratio of the diluent and coupling agent be (3~
6):1。
23. composition according to claim 1, which is characterized in that the length of the glass fibre is 0.5mm-10mm.
24. composition according to claim 23, which is characterized in that the length of the glass fibre is 1mm-3mm, or
3mm-5mm or 5mm-7mm.
25. -24 described in any item compositions according to claim 1, which is characterized in that the weight of each component in the composition
Percentage composition are as follows: super high molecular weight ultra-fine grain diameter acrylic polymers 10-95wt%, glass fibre 5-90wt%.
26. composition according to claim 25, which is characterized in that in the composition, the content of the glass fibre
For 10-80wt%.
27. composition according to claim 26, which is characterized in that in the composition, the content of the glass fibre
For 40-70wt%.
28. a kind of sheet material, which is characterized in that the sheet material is prepared by the described in any item compositions of claim 1-27.
29. a kind of pipe, which is characterized in that pipe sheet material as described in claim 28 is prepared.
30. pipe according to claim 29, which is characterized in that the wall thickness of the pipe is between 0.1mm-10mm.
31. pipe according to claim 30, which is characterized in that the wall thickness of the pipe is between 0.5mm-5mm.
32. the preparation method of sheet material described in claim 28, which is characterized in that the described method comprises the following steps: will be described
Super high molecular weight ultra-fine grain diameter acrylic polymers and the glass fibre are uniformly mixed in high-speed mixer, and extruder is added
In, it is squeezed out by sheet die, through cooling, stretches, the sheet material is made.
33. the preparation method of the described in any item pipes of claim 29-31, which is characterized in that the described method comprises the following steps:
The super high molecular weight ultra-fine grain diameter acrylic polymers and the glass fibre are uniformly mixed in high-speed mixer, is added and squeezes
It out in machine, is squeezed out by pipe mold, through cooling, stretches, the pipe is made.
34. the purposes of sheet material described in claim 28, which is characterized in that the sheet material is used for automobile, field of electronic devices.
35. the purposes of the described in any item pipes of claim 29-31, which is characterized in that the pipe is used for water supply and drainage, petroleum drilling
Spy field.
36. purposes according to claim 35, which is characterized in that the pipe is as water supply and drainage pipe or mining wear resistance pipe.
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| CN201610694926.4A CN106279989B (en) | 2016-08-19 | 2016-08-19 | Glass fiber reinforcement prolylene polymer composition, sheet material prepared therefrom or pipe and its application |
| PCT/CN2017/075496 WO2018032745A1 (en) | 2016-08-19 | 2017-03-02 | Ultra-high molecular weight, ultra-fine particle size propene polymer, preparation method therefor and use thereof |
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