CN107245194A - A kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin - Google Patents
A kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin Download PDFInfo
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- CN107245194A CN107245194A CN201710244797.3A CN201710244797A CN107245194A CN 107245194 A CN107245194 A CN 107245194A CN 201710244797 A CN201710244797 A CN 201710244797A CN 107245194 A CN107245194 A CN 107245194A
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- preparation
- high strength
- heat resistant
- strength heat
- atactic copolymerized
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin, comprise the following steps：The preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress first paragraph reaction, the reaction pressure for controlling reactor is 2.2 ~ 2.4MPa, and 63 ~ 69 DEG C of reaction temperature adds hydrogen and 3 ~ 4% ethylene reactions that concentration is 4100 ~ 4300ppm；Then second segment reaction is carried out, the reaction pressure for controlling reactor is 2.1 ~ 2.3MPa, 63 ~ 69 DEG C of reaction temperature adds propylene, hydrogen and ethene, and 3900 ~ 4100ppm of density of hydrogen, ethene adds concentration 1 ~ 3%, finally gives polypropylene powder；Antioxidant, acid-acceptor and processing aid are added into the basic powder of the polypropylene, after being well mixed, extruding pelletization obtains high strength heat resistant atactic copolymerized polypropene resin material.Acrylic resin obtained by the present invention has higher intensity and heat-resist.
Description
Technical field
The present invention relates to a kind of preparation method of acrylic resin, more particularly to a kind of high strength heat resistant random copolymerization poly- third
The preparation method of olefine resin.
Background technology
At present, aluminium-plastic pipe, pvc pipe and the PE pipes that domestic households are used all have obvious shortcoming.Aluminium-plastic pipe uses pressure
Compact form is connected, easily leak after long-time.Pvc pipe General Life only has 15 years, and pvc pipe and PE pipes be not used to 70 DEG C with
Upper high-temperature-hot-water.The tubing that common atactic copolymerized polypropene resin is made at present is also that service life is unable to reach 50 years, is not inconsistent
Close《GB/T 18742-2002 hot and cold waters polypropylene pipe systems》Requirement.
The content of the invention
It is an object of the invention to provide a kind of high strength heat resistant atactic copolymerized polypropene process for preparing resins.Obtained by this method
Acrylic resin there is higher intensity and heat-resist, the pipe part being made can carry out sweat soldering, and convey
70 DEG C of high temperature above hot water, can reach《GB/T 18742-2002 hot and cold waters polypropylene pipe systems》50 years of middle requirement make
Use the life-span.
The purpose of the present invention is to be achieved through the following technical solutions：A kind of high strength heat resistant atactic copolymerized polypropene resin
Preparation method, comprise the following steps：
(1) preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress
First paragraph reacts, and the reaction pressure for control reactor is 2.2 ~ 2.4MPa, 63 ~ 69 DEG C of reaction temperature, add concentration for 4100 ~
4300ppm hydrogen and 3 ~ 4% ethylene reactions；Then carry out second segment reaction, control reactor reaction pressure be 2.1 ~
2.3MPa, 63 ~ 69 DEG C of addition propylene of reaction temperature, hydrogen and ethene, 3900 ~ 4100ppm of density of hydrogen, ethene addition concentration 1 ~
3%, melt flow rate (MFR) is finally given for 0.2 ~ 0.3g/10min, bonding ethylene content is 4~6%, weight average molecular weight is 60 ~ 80
Ten thousand, molecular weight distribution is 4 ~ 6 polypropylene powder；
(2) toward addition antioxidant, acid-acceptor and processing aid in the basic powder of the polypropylene, after being well mixed, extrusion is made
Grain, obtains high strength heat resistant atactic copolymerized polypropene resin material.
The extruding pelletization temperature of step (2) of the present invention is 210 ~ 230 DEG C.
In the step (2), on the basis of polyacrylic amount, the mass ratio between the raw material is：
The ﹕ 0.5 ~ 1 of Ju Bing Xi Shu Zhi ﹕ antioxidant=100
The ﹕ 0.05 ~ 0.15 of Ju Bing Xi Shu Zhi ﹕ acid-acceptors=100
The ﹕ 0.03 ~ 0.1 of Ju Bing Xi Shu Zhi ﹕ processing aids=100.
Catalyst INcat CDi of the present invention have the highest polymerization activity of forth generation catalyst.CDi catalyst has
Just like properties：Controlled morphologies, super-active and very high selectivity.The resin size narrowly distributing produced, catalyst
Remaining minimum, non-corrosiveness, color and luster is fabulous, and smell is few, controllable stereoregularity and high-consistency.This high activity promotes reactor output
High, process simplification, so as to reduce capital investment and running cost.
Co-catalyst of the present invention：TEAL, modifying agent DIBDMS.
Antioxidant of the present invention is 3-（Double tertiary butyl -4- the hydroxy-cyclohexyls of 3,5-）Propionic ester (1010), three（2,4-
Di-tert-butyl-phenyl）Phosphite ester (168) and (3,5- di-tert-butyl-4-hydroxyl benzyls) mesitylene of 2,4,6- tri- (330)
Combination.
Acid-acceptor of the present invention is calcium stearate.
Processing aid of the present invention is fluoropolymer, specifically there is the FX3966 of Nanjing Te Su Science and Technology Ltd.s,
FX5927, FX5926, FX5922, FX5920, FX5924 of 3M companies.
The present invention has the advantages that compared with prior art：
(1) the shock resistance effect for the high strength heat resistant atactic copolymerized polypropene resin that the present invention is provided is improved than plain polypropylene
20~100%.By resin Maoming Petrochemical T4401 simply supported beam notch impact strengths 60kJ/m produced by the invention2More than, common poly- third
Olefine resin such as Maoming Petrochemical K8003 simply supported beams notch impact strength 40kJ/m2, Maoming Petrochemical Z30S simply supported beam notch impact strengths
30kJ/m2,
(2) product quality for preparing of the present invention, which can reach, only adds a small amount of color masterbatch and just can directly be molded pipe part.Nothing of the present invention
Other additives need to be added again can just obtain good anti-impact heat resistance.
(3) product prepared by the present invention has passed through《GB/T 17219-1998 Drinking Water transmission ＆ distribution wetting systems and protection
The safety evaluation standard of material》、《The food packaging acrylic resin sanitary standards of GB 9693-88》、《FDA 21 CFR
177.1520 food contact material safety detections》Certification.
(4) pipe part that product prepared by the present invention is made can convey more than 70 DEG C of high-temperature-hot-water, the pipe of production
Material pipe fitting connected mode is sweat soldering, is used for a long time water-tight.
Embodiment
Illustrate present invention in further detail by the following examples, but following embodiments are only intended to the present invention
Content be illustrated, rather than limitation is therefore any in the implication and scope suitable with claims of the present invention
Change, be all considered as being included within the scope of the claims.
Embodiment 1
The preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress first
Duan Fanying, control reactor reaction pressure be 2.2 ~ 2.4MPa, 63 ~ 69 DEG C of reaction temperature, add concentration be 4100 ~
4300ppm hydrogen and 3 ~ 4% ethylene reactions.Then, carry out second segment reaction, control reactor reaction pressure be 2.1 ~
2.3MPa, 63 ~ 69 DEG C of addition propylene of reaction temperature, hydrogen and ethene, 3900 ~ 4100ppm of density of hydrogen, ethene addition concentration 1 ~
3%, melt flow rate (MFR) is finally given for 0.28g/10min, and bonding ethylene content is 4.18% polypropylene powder.
Embodiment 2
The preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress first
Duan Fanying, control reactor reaction pressure be 2.2 ~ 2.4MPa, 63 ~ 69 DEG C of reaction temperature, add concentration be 4100 ~
4300ppm hydrogen and 3 ~ 4% ethylene reactions.Then, carry out second segment reaction, control reactor reaction pressure be 2.1 ~
2.3MPa, 63 ~ 69 DEG C of addition propylene of reaction temperature, hydrogen and ethene, 3900 ~ 4100ppm of density of hydrogen, ethene addition concentration 1 ~
3%, melt flow rate (MFR) is finally given for 0.26g/10min, and bonding ethylene content is 4.26% polypropylene powder.
Embodiment 3
The preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress first
Duan Fanying, control reactor reaction pressure be 2.2 ~ 2.4MPa, 63 ~ 69 DEG C of reaction temperature, add concentration be 4100 ~
4300ppm hydrogen and 3 ~ 4% ethylene reactions.Then, carry out second segment reaction, control reactor reaction pressure be 2.1 ~
2.3MPa, 63 ~ 69 DEG C of addition propylene of reaction temperature, hydrogen and ethene, 3900 ~ 4100ppm of density of hydrogen, ethene addition concentration 1 ~
3%, melt flow rate (MFR) is finally given for 0.26g/10min, and bonding ethylene content is 4.28% polypropylene powder.
The catalyst INcat CDi used in embodiment 1 ~ 3 have the highest polymerization activity of forth generation catalyst.CDi is urged
Agent has the property that：Controlled morphologies, super-active and very high selectivity.The resin size narrowly distributing produced,
Catalyst residue is minimum, and non-corrosiveness, color and luster is fabulous, and smell is few, controllable stereoregularity and high-consistency.This high activity promotes reaction
Device yield is high, process simplification, so as to reduce capital investment and running cost.Co-catalyst is TEAL and modifying agent
DIBDMS。
Catalyst CDi consumptions are 20-30g/t, and the consumption TEAL of co-catalyst is 100g-150/t, and DIBDMS is 50-
150g/t。
The basic powder of polypropylene, acid-acceptor, processing aid and antioxidant prepared by embodiment 1 ~ 3 presses following mass ratio respectively
After well mixed, in 210 ~ 230 DEG C of extruding pelletizations, high strength heat resistant atactic copolymerized polypropene resin material experimental example is obtained respectively
1~3。
The ﹕ 0.7 of Ju Bing Xi Shu Zhi ﹕ antioxidant=100
The ﹕ 0.1 of Ju Bing Xi Shu Zhi ﹕ acid-acceptors=100
The ﹕ 0.05 of Ju Bing Xi Shu Zhi ﹕ processing aids agent=100.
The described antioxidant of experimental example 1 ~ 3 is 3-（Double tertiary butyl -4- the hydroxy-cyclohexyls of 3,5-）Propionic ester (1010), three
（2,4- di-tert-butyl-phenyls）Phosphite ester (168) and 2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) mesitylene
(330) combination.Acid-acceptor is calcium stearate.Processing aid is fluoropolymer, specifically there is Nanjing Te Su Science and Technology Ltd.s
FX3966 and 3M companies FX5927, FX5926, FX5922, FX5920, FX5924.
Take K8003, PPB-M02D and PPB- of the polyacrylic resin material and Maoming Petrochemical in above-mentioned experimental example 1 ~ 3
MT25-S carries out performance comparison, as a result referring to table 1.
As it can be seen from table 1 K8003, PPB-M02D and PPB-MT25-S that experimental example 1 ~ 3 compares Maoming Petrochemical have more preferably
Simply supported beam notch impact strength and load deformation temperature performance.
Claims (7)
1. a kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin, it is characterized in that, comprise the following steps：
(1) preparation of acrylic resin：Added by raw material of propylene in reactor, and add catalyst and co-catalyst progress
First paragraph reacts, and the reaction pressure for control reactor is 2.2 ~ 2.4MPa, 63 ~ 69 DEG C of reaction temperature, add concentration for 4100 ~
4300ppm hydrogen and 3 ~ 4% ethylene reactions；Then carry out second segment reaction, control reactor reaction pressure be 2.1 ~
2.3MPa, 63 ~ 69 DEG C of addition propylene of reaction temperature, hydrogen and ethene, 3900 ~ 4100ppm of density of hydrogen, ethene addition concentration 1 ~
3%, melt flow rate (MFR) is finally given for 0.2 ~ 0.3g/10min, bonding ethylene content is 4~6%, weight average molecular weight is 60 ~ 80
Ten thousand, molecular weight distribution is 4 ~ 6 polypropylene powder；
(2) toward addition antioxidant, acid-acceptor and processing aid in the basic powder of the polypropylene, after being well mixed, extruding pelletization,
Obtain high strength heat resistant atactic copolymerized polypropene resin material.
2. the preparation method of high strength heat resistant atactic copolymerized polypropene resin according to claim 1, it is characterized in that, it is described
In step (2), on the basis of polyacrylic amount, the mass ratio between the raw material is：
The ﹕ 0.5 ~ 1 of Ju Bing Xi Shu Zhi ﹕ antioxidant=100
The ﹕ 0.05 ~ 0.15 of Ju Bing Xi Shu Zhi ﹕ acid-acceptors=100
The ﹕ 0.03 ~ 0.1 of Ju Bing Xi Shu Zhi ﹕ processing aids=100.
3. the preparation method of high strength heat resistant atactic copolymerized polypropene resin according to claim 2, it is characterized in that, it is described
In step (1), catalyst is INcat CDi, and co-catalyst is TEAL and/or modifying agent DIBDMS.
4. the preparation method of the high strength heat resistant atactic copolymerized polypropene resin according to claim 1 or 2 or 3, its feature
It is that described processing aid is fluoropolymer.
5. the preparation method of high strength heat resistant atactic copolymerized polypropene resin according to claim 4, it is characterized in that, it is described
Antioxidant be 3-（Double tertiary butyl -4- the hydroxy-cyclohexyls of 3,5-）Propionic ester, three（2,4- di-tert-butyl-phenyls）Phosphite ester and
The combination of 2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) mesitylene.
6. the preparation method of high strength heat resistant atactic copolymerized polypropene resin according to claim 4, it is characterized in that, it is described
Acid-acceptor be calcium stearate.
7. the preparation method of high strength heat resistant atactic copolymerized polypropene resin according to claim 4, it is characterized in that, it is described
The extruding pelletization temperature of step (2) is 210 ~ 230 DEG C.
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| CN201710244797.3A CN107245194B (en) | 2017-04-14 | 2017-04-14 | Preparation method of high-strength heat-resistant random copolymerization polypropylene resin |
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| CN201710244797.3A CN107245194B (en) | 2017-04-14 | 2017-04-14 | Preparation method of high-strength heat-resistant random copolymerization polypropylene resin |
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Cited By (2)
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| CN108003479A (en) * | 2017-12-07 | 2018-05-08 | 广州赫尔普化工有限公司 | A kind of random copolymerization polypropylene pipe compound additive |
| CN109553863A (en) * | 2018-10-09 | 2019-04-02 | 中国石油化工股份有限公司 | It is a kind of to squeeze out with polypropylene material and preparation method thereof |
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