CN112500641A - Modified polypropylene composite material and preparation method thereof - Google Patents
Modified polypropylene composite material and preparation method thereof Download PDFInfo
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- CN112500641A CN112500641A CN202011529240.2A CN202011529240A CN112500641A CN 112500641 A CN112500641 A CN 112500641A CN 202011529240 A CN202011529240 A CN 202011529240A CN 112500641 A CN112500641 A CN 112500641A
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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
- 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
- C08L23/12—Polypropene
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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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08K2201/003—Additives being defined by their diameter
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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
- 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
- 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
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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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- 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
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses a modified polypropylene composite material which is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 14250.05-0.2 part of antioxidant, 6190.02-0.05 part of antioxidant, 1680.1-0.5 part of antioxidant, 10-30 parts of glass fiber, 0.2-0.5 part of liquid paraffin, KH 5500.2-1 part of ethylene-octene copolymer, 5-30 parts of TMB-50.2-0.5 part of grafting auxiliary agent and 0.5-1.5 part of grafting auxiliary agent. The grafting auxiliary agent is a mixture of tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 3-5. According to the invention, the aging resistance, acid and alkali resistance of the polypropylene are synergistically improved by taking a mixture of a specific compound antioxidant, a specific beta nucleating agent, tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate as a grafting aid.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a modified polypropylene composite material and a preparation method thereof.
Background
Polypropylene is a general thermoplastic with excellent comprehensive performance, has the characteristics of low price, light weight, solvent resistance, good elasticity, rigidity, easy recovery, no toxicity and the like, is the most important light material for automobiles, can reduce the mass of automobile parts by about 40 percent, can reduce the purchase cost by about 40 percent, and is widely adopted in the field of automobile parts. The modified polypropylene is prepared by refining polypropylene and various organic and inorganic materials by a special compounding technology, is widely applied to various industries such as chemical industry, materials, buildings and the like, and is closely related to the daily life of people.
When the polypropylene material is used as a container product for contacting or storing acid and alkali chemicals, especially in places with higher temperature, the polypropylene material can be degraded to different degrees under the action of the acid and alkali chemicals, heat, oxygen and other factors, and the physical properties, the mechanical properties, the appearance color, the use function and other aspects of the product are directly and negatively influenced. At present, the prior art has disclosed many technical proposals related to polypropylene materials, for example, chinese patent application with publication No. CN 104250394A discloses a modified polypropylene material and a preparation method thereof, which is prepared from 100 parts of polypropylene, 0.01-0.05 part of antioxidant 1425, 0.01-0.05 part of antioxidant 619, 0.01-0.05 part of antioxidant 1035, 0-100 parts of filler, 0-1 part of lubricant, 0-1 part of coupling agent, and 0-30 parts of toughening agent. According to the invention, three combined antioxidants are added to modify the polypropylene material, so that the hydrolysis resistance and the aging resistance of the polypropylene are improved, the mechanical stability and the color stability of the material at a higher processing temperature or a higher using temperature can be maintained for a long time, and the total addition of the antioxidants is reduced, thereby saving the modification cost of the polypropylene. However, the modified polypropylene material has large reduction amplitude of mechanical strength for the use occasions contacting high-temperature chemical acid-base liquid for a long time, and can not meet the use requirements. Therefore, research and development of the modified polypropylene composite material which can be used in a high-temperature acid-base environment for a long time has important application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified polypropylene composite material with high strength and acid and alkali resistance and a preparation method thereof. In order to realize the purpose, the invention adopts the following technical scheme:
a modified polypropylene composite material is prepared from the following raw materials in parts by weight:
100 portions of polypropylene
14250.05-0.2 parts of antioxidant
6190.02-0.05 part of antioxidant
1680.1-0.5 part of antioxidant
10-30 parts of glass fiber
0.2 to 0.5 portion of liquid paraffin
KH 5500.2-1 parts
5-30 parts of ethylene-octene copolymer
TMB-50.2-0.5 part
0.5-1.5 parts of grafting auxiliary agent
The glass fiber is alkali-free chopped glass fiber, the length of the glass fiber is 2-15mm, and the diameter of the glass fiber is 6-25 mu m;
the melt flow rate (190 ℃ x 2.16kg) of the ethylene-octene copolymer is 0.2-10g/10 min;
the grafting auxiliary agent is a mixture of tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 3-5;
the preparation method of the modified polypropylene composite material comprises the following steps:
(1) weighing the raw materials in parts by weight, and placing the raw materials in a mixer to stir and mix for 3-5 minutes to obtain a mixture;
(2) the mixture is sent into a double-screw or reciprocating single-screw extrusion device to be melted, blended and extruded for granulation at the temperature of 180-235 ℃, the length-diameter ratio of the adopted double-screw extrusion device is 32-40, the rotating speed of the screw is 600 revolutions per minute, the working temperature of the double-screw extrusion is 180-200 ℃ in the first zone, 200-230 ℃ in the second zone, 200-230 ℃ in the third zone, 200-230 ℃ in the fourth zone, the residence time of the whole extrusion process is lmin-2min, and the pressure is 21-25 MPa.
According to the invention, the prior art is improved, and the antioxidant 1425, the antioxidant 619 and the antioxidant 168 are jointly used as a compound antioxidant to synergistically improve the heat resistance and the aging resistance of polypropylene; TMB-5 is adopted as a specific beta nucleating agent, so that the crystallization density of the polypropylene is improved, the crystal size of a polymer spherulite structure is promoted to be smaller, the structure is more uniform, and the crystallization performance of the polypropylene is greatly improved; the mixture of the tripropylene glycol diacrylate phthalate and the ethoxylated trimethylolpropane triacrylate is used as a specific grafting aid and can form hydrogen bonds with the surface of the inorganic filler, so that the two-phase interface is combined more tightly, the interface compatibility of the polypropylene and the inorganic filler is improved, and oxygen and acid-base molecules can be effectively prevented from freely diffusing from the surface of a sample to the interior. In conclusion, the aging resistance, the acid and alkali resistance of the polypropylene are synergistically improved by taking the mixture of the specific compound antioxidant, the specific beta nucleating agent, the tripropylene glycol diacrylate phthalate and the ethoxylated trimethylolpropane triacrylate as the grafting aid.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims.
Example 1:
a modified polypropylene composite material is prepared from the following raw materials in parts by weight:
100 portions of polypropylene
14250.1 parts of antioxidant
6190.03 parts of antioxidant
1680.2 parts of antioxidant
20 portions of glass fiber
0.5 part of liquid paraffin
KH 5501 parts
Ethylene-octene copolymer 15 parts
TMB-50.3 parts
Grafting assistant 1 part
The polypropylene is Shanghai lithification M700R;
the glass fiber is alkali-free chopped glass fiber, the length of the glass fiber is 2mm, and the diameter of the glass fiber is 10 mu m;
the ethylene-octene copolymer has a melt flow rate (190 ℃ C.. times.2.16 kg) of 0.5g/10 min;
the grafting auxiliary agent is a mixture of tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 3.
the preparation method of the modified polypropylene composite material comprises the following steps:
(1) weighing the raw materials in parts by weight, and placing the raw materials in a mixer to stir and mix for 5 minutes to obtain a mixture;
(2) and (2) feeding the mixture into a double-screw extrusion device for melt blending, extrusion and granulation, wherein the length-diameter ratio of the adopted double-screw extrusion device is 32, the screw rotation speed is 300 r/min, the double-screw extrusion working temperature is 190 ℃ in the first zone, 200 ℃ in the second zone, 220 ℃ in the third zone, 220 ℃ in the fourth zone, the residence time in the whole extrusion process is 2min, and the pressure is 22 MPa.
Comparative example 1:
the only difference between the preparation method of the modified polypropylene composite material and the embodiment 1 is that the TMB-5 is replaced by the calcium pimelate.
Comparative example 2:
a modified polypropylene composite was prepared as in example 1, except that di (p-methylbenzylidene) sorbitol was used in place of TMB-5.
Comparative example 3:
the only difference between the preparation method of the modified polypropylene composite material and the embodiment 1 is that TMB-5 is replaced by 2,2' -methylene bis (4, 6-di-tert-butylphenyl) aluminum phosphate.
Comparative example 4:
a modified polypropylene composite material is prepared by the same method as in example 1, the only difference is that the antioxidant 1035 is used for replacing the antioxidant 168, and the amount is changed to 0.05 part.
Comparative example 5:
the preparation method of the modified polypropylene composite material is the same as that in example 1, and the only difference is that the grafting auxiliary agent is pentaerythritol triacrylate.
Comparative example 6:
the only difference between the preparation method of the modified polypropylene composite material and the embodiment 1 is that the grafting auxiliary agent is changed into 1, 4-butanediol diacrylate.
Comparative example 7:
the only difference between the preparation method of the modified polypropylene composite material and the embodiment 1 is that the grafting auxiliary agent is changed into 1, 6-hexanediol diacrylate.
Comparative example 8:
the preparation method of the modified polypropylene composite material is the same as that in example 1, the only difference is that the grafting auxiliary agent is changed into a mixture of diethylene glycol diacrylate and trimethylolpropane triacrylate, and the mass ratio of the diethylene glycol diacrylate to the trimethylolpropane triacrylate is 1: 1.
comparative example 9:
the preparation method of the modified polypropylene composite material is the same as that of the example 1, and the only difference is that the grafting auxiliary agent
The adhesive is a mixture of tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate, wherein the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 1.
comparative tests on the properties of the modified polypropylene composites obtained in inventive example 1 and comparative examples 1 to 9:
1. determination of tensile Properties of plastics according to GB/T1040.1-2006 part 1: the tensile strength (MPa) was measured in general rules, and the tensile rate was 50 mm/min.
2. The bending strength (MPa) is tested according to GB/T9341-2008 & ltdetermination of Plastic bending Properties & gt, and the size of a sample is as follows: 80 mm. times.10 mm. times.4 mm, and the bending speed was 2 mm/min.
3. The performance of the plastic liquid-resistant chemical reagent is tested according to GB/T11547-2008 'determination of the performance of the plastic liquid-resistant chemical reagent', and hydrochloric acid with the mass fraction of 20% is soaked for one week at the constant temperature of 85 ℃.
The acid and alkali resistance of the polypropylene composite material is represented by a strength change rate, namely, the change percentage of a performance value after soaking relative to a performance value before soaking is represented as follows:
change in Strength = (X1-X2)/X1X 100%
Wherein, X1-corresponding Pre-soak Performance value;
x2-value of a property after soaking.
The test results are shown in table 1.
TABLE 1
As can be seen from the test results in Table 1, the modified polypropylene composite material of example 1 of the present invention has very excellent tensile strength, bending strength and hot hydrochloric acid corrosion resistance, and at the same time, the tensile strength, bending strength and hot hydrochloric acid corrosion resistance are greatly reduced by the performance influence caused by the different types of the nucleating agents of comparative examples 1-3 and example 1; the tensile strength, the bending strength and the hot hydrochloric acid corrosion resistance are reduced to different degrees through the performance influence caused by different types and dosages of the antioxidant in the comparative example 4 and the example 1; the tensile strength, the bending strength and the hot hydrochloric acid corrosion resistance are reduced to different degrees by the performance influence caused by different types and proportions of the grafting aids of comparative examples 5 to 9 and example 1. Therefore, the aging resistance, the acid and alkali resistance of the polypropylene are synergistically improved by taking the mixture of the specific compound antioxidant composition, the specific beta nucleating agent, the tripropylene glycol diacrylate phthalate and the ethoxylated trimethylolpropane triacrylate as a grafting aid.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. That is, all equivalent changes and modifications made according to the content of the claims of the present invention should be within the technical scope of the present invention.
Claims (2)
1. The modified polypropylene composite material is characterized by being prepared from the following raw materials in parts by weight:
100 portions of polypropylene
14250.05-0.2 parts of antioxidant
6190.02-0.05 part of antioxidant
1680.1-0.5 part of antioxidant
10-30 parts of glass fiber
0.2 to 0.5 portion of liquid paraffin
KH 5500.2-1 parts
5-30 parts of ethylene-octene copolymer
TMB-50.2-0.5 part
0.5-1.5 parts of grafting auxiliary agent
The glass fiber is alkali-free chopped glass fiber, the length of the glass fiber is 2-15mm, and the diameter of the glass fiber is 6-25 mu m;
the melt flow rate (190 ℃ x 2.16kg) of the ethylene-octene copolymer is 0.2-10g/10 min;
the grafting auxiliary agent is a mixture of tripropylene glycol diacrylate phthalate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1: 3-5.
2. The method for preparing the modified polypropylene composite material according to claim 1, comprising the following steps:
(1) weighing the raw materials in parts by weight, and placing the raw materials in a mixer to stir and mix for 3-5 minutes to obtain a mixture;
(2) the mixture is sent into a double-screw or reciprocating single-screw extrusion device to be melted, blended and extruded for granulation at the temperature of 180-235 ℃, the length-diameter ratio of the adopted double-screw extrusion device is 32-40, the rotating speed of the screw is 600 revolutions per minute, the working temperature of the double-screw extrusion is 180-200 ℃ in the first zone, 200-230 ℃ in the second zone, 200-230 ℃ in the third zone, 200-230 ℃ in the fourth zone, the residence time of the whole extrusion process is lmin-2min, and the pressure is 21-25 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011529240.2A CN112500641A (en) | 2020-12-22 | 2020-12-22 | Modified polypropylene composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011529240.2A CN112500641A (en) | 2020-12-22 | 2020-12-22 | Modified polypropylene composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
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| CN112500641A true CN112500641A (en) | 2021-03-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011529240.2A Withdrawn CN112500641A (en) | 2020-12-22 | 2020-12-22 | Modified polypropylene composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850866A (en) * | 2022-12-29 | 2023-03-28 | 上海宏盎新材料科技有限公司 | Lightweight automobile door plate modified polypropylene material and preparation method thereof |
-
2020
- 2020-12-22 CN CN202011529240.2A patent/CN112500641A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850866A (en) * | 2022-12-29 | 2023-03-28 | 上海宏盎新材料科技有限公司 | Lightweight automobile door plate modified polypropylene material and preparation method thereof |
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Application publication date: 20210316 |