CN114369314B - Polypropylene composite material capable of improving die sticking, high in performance and thin in wall and preparation method thereof - Google Patents
Polypropylene composite material capable of improving die sticking, high in performance and thin in wall and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
Abstract
The invention discloses a polypropylene composite material capable of improving die bonding, high performance and thinning and a preparation method thereof, which comprises the following raw materials in parts by weight: polypropylene: 57-75; functional talcum powder master batch: 14-28; an elastomer: 8-17; an antioxidant: 0-1; other auxiliary agents: 0-3; the invention has the advantages that: the invention adopts a high-efficiency functional talcum powder master batch to replace the traditional modified polypropylene formulation to directly use talcum powder and auxiliary agent to prepare materials in the formulation design of the thinned polypropylene composite material, the functional talcum powder master batch uses high-fluidity polypropylene as a carrier, when the polymer system is extruded from a double screw extrusion or injection molding machine, high-mesh talcum powder and elastomer can be well dispersed into the composite material system, and simultaneously, the composite lubricant in the functional talcum powder master batch can move to the outer side of a material melt at first and be enriched on the surface layer of the material, thereby improving the lubricating performance of the whole material system.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and processing thereof, and relates to a polypropylene composite material with improved die bonding, high performance and thin wall and a preparation method thereof.
Background
With the rapid development of the automobile industry and the increasing severity of environmental problems, various major automobile factories are devoted to the related study of the weight reduction of the whole automobile. For polypropylene plastic parts with the largest automobile use, a thin-wall design is favored in the technical means of light weight of the whole automobile. At present, the traditional wall thickness of the automobile plastic parts for commercial use in various major automobile factories is 2.5-3.0mm, and the wall thickness of the automobile plastic parts after the thin-wall design reaches 1.8-2.2mm. After the wall thickness of the part is thinned, in order to ensure that the appearance and performance of the part are not lost, the thinned part is made of a material with high rigidity, high toughness and high fluidity which is typical in comparison with the traditional wall thickness part, so that the thinned part is cooperatively realized by selecting a proper polypropylene base material, a high-performance filler and an elastomer toughening agent in terms of formulation.
At present, the thinned polypropylene material is widely applied to inner and outer ornaments of automobile uprights, door plates, instrument panels, bumpers and the like, when thin-wall parts with complex structures, larger sizes and longer processes are encountered, such as thin-wall bumper parts, the thinner the wall thickness of the part local position is, the material melt is easily influenced by strong flow shearing force at the position with thinner wall thickness, certain surface displacement can be caused to occur to the material, after pressure maintaining is carried out, the surface layer of the part is tightly attached to the surface of a mold, a certain sticking phenomenon can occur during demolding, the appearance of the part is seriously influenced, and particularly, the rising of the mold temperature along with the lengthening of the part injection molding time is aggravated, so that the continuous production of the part is unfavorable. Therefore, the method has important significance on solving the problem of sticking the thin-walled part in the injection molding production process.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a polypropylene composite material with improved die bonding, high performance and thinned wall and a preparation method thereof. So as to solve the technical problems in the prior art. In the method, in the formula design of the thinned polypropylene composite material, functional talcum powder master batch is adopted to replace the traditional formula to directly add auxiliary agents such as talcum powder, lubricant and the like so as to realize the improvement of the lubricating performance of the composite material system; the functional talcum powder master batch consists of high-flow polypropylene, an elastomer, high-mesh talcum powder, a composite lubricant, a coupling agent and the like; the composite lubricant is prepared by compounding ethylene bis-stearylamide and stearate in a ratio of 1:1, and has good internal and external lubrication effects; the coupling agent is titanate coupling agent, can form a covering film on the surface of talcum powder, improves the original hydrophilic property of talcum powder, and can improve the interfacial binding force and compatibility between talcum powder and polypropylene, thereby improving the comprehensive mechanical property of a polypropylene composite material system; meanwhile, the functional talcum powder master batch takes high-fluidity polypropylene as a carrier, when a polymer system is extruded from a double-screw extrusion or injection molding machine, high-mesh talcum powder and elastomer can be well and evenly dispersed into a composite material system, and meanwhile, a composite lubricant can move to the outer side of a material melt at first and be enriched on the surface layer of the material, so that the lubricity of the composite material system is improved, and the problem of sticking the material in the injection molding production process is solved; in addition, the talcum powder with high mesh number preferably has the characteristic of regular lamellar structure, can utilize the interlayer gap to adsorb odor micromolecules generated in the extrusion production process of the curing material, can reduce the odor emission performance of a composite material system, and meanwhile, the regular lamellar structure is beneficial to interlayer sliding, is helpful for wetting and mixing after the injection molding of the composite material, and can play a synergistic effect together with a composite lubricant to improve the sticking problem.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the high-performance thin-wall polypropylene composite material capable of improving the sticking of the die comprises the following raw materials in parts by weight:
polypropylene: 57-75;
functional talcum powder master batch: 14-28;
an elastomer: 8-17;
an antioxidant: 0-1;
other auxiliary agents: 0-3.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the polypropylene matrix resin adopts one or two mixtures of high-fluidity copolymerized polypropylene, and the melt index (230 ℃ and 2.16 KG) is about 60g-100g/10min.
The functional talcum powder master batch is prepared from the following components in parts by weight: 10 parts of high-flow polypropylene, 15 parts of elastomer, 71.5 parts of high-mesh talcum powder, 1.5 parts of composite lubricant and 2 parts of coupling agent. Wherein the high fluidity polypropylene has a melt index (230 ℃,2.16 KG) of about 60-100g/10 min; the elastomer is an ethylene and octene copolymer; the high-mesh talcum powder is 10000-mesh talcum powder with a specific regular lamellar structure; the composite lubricant is prepared by compounding ethylene bis-stearylamide and stearate in a ratio of 1:1, wherein the ethylene bis-stearylamide is N, N_ethylene bis-stearylamide, and the stearate is one of calcium stearate and magnesium stearate; the coupling agent is titanate coupling agent.
The elastomer is an ethylene and octene copolymer with a density of 0.86-0.90g/cm 3 The melt index is 0.5-6g/10min.
The antioxidant is an antioxidant considered to be required by a person skilled in the art, and is mainly composed of one or more than two of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), stearyl thiodipropionate (antioxidant DSTP), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester (antioxidant 1076).
The other auxiliary agents are one or a combination of a plurality of various color components, light stabilizers, processing aids and the like which are considered to be needed by the person skilled in the art.
The preparation method of the polypropylene composite material with improved die sticking, high performance and thinned wall comprises the following steps:
A. preparing functional talcum powder master batch:
adding high-flow polypropylene, an elastomer, high-mesh talcum powder, a composite lubricant and a coupling agent into a high-speed mixer according to weight components, uniformly mixing, transferring into a mixing chamber of an internal mixer for high-speed banburying and mixing, transferring the banburying and mixing block materials into a double-wrist feeding port for feeding, and extruding, air-cooling and granulating by a single-screw extruder to prepare the functional talcum powder master batch. Wherein the temperature of a banburying chamber in the banburying machine is set at 170-190 ℃, the diameter of a single screw is 70mm, the length-diameter ratio is 12, the single screw extruder is divided into three sections, the temperature is controlled, and the temperature from a feeding port to each section of a machine head is 180 ℃, 200 ℃ and 210 ℃ in sequence.
B. The demolding, high-performance and thin-wall polypropylene composite material is improved, and the preparation method thereof is as follows:
(1) Weighing the components according to the mass ratio;
(2) Placing the components such as polypropylene, functional talcum powder master batch, elastomer, antioxidant and other auxiliary agents into a high-speed mixer for high-speed mixing for 5-10min;
(3) Adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, carrying out melt extrusion, bracing, cooling and granulating, and then carrying out material drying treatment to prepare the polypropylene composite material with improved demoulding, high performance and thinned wall, wherein the processing process temperatures of all areas of the double-screw extruder are as follows: a region: 180-205 ℃, 190-205 ℃ in the second region, 210-215 ℃ in the third region, 205-210 ℃ in the fourth region and 190-200 ℃ in the machine head. The whole extrusion process is carried out for about 2 minutes under the pressure of 12-18Mpa, the rotation speed of a main screw is 500-800r/min, the temperature of a water tank is 30-60 ℃, double vacuum pumping is added at two sides of a double screw extruder, the vacuum degree of double vacuum is-0.07 MPa to-0.08 MPa, and a material drying process is adopted for material drying: and (3) storing materials in a tank A, drying materials in a tank B, and cooling the tank C, wherein the tank B is subjected to a material drying process: 130 ℃ 4H.
The invention has the advantages that:
(1) According to the invention, in the formula design of the thinned polypropylene composite material, a high-efficiency functional talcum powder master batch is adopted to replace the traditional modified polypropylene formula to directly use talcum powder and an auxiliary agent for material preparation, the functional talcum powder master batch uses high-fluidity polypropylene as a carrier, when a polymer system is extruded from a double screw extruder or an injection molding machine, high-mesh talcum powder and an elastomer can be well dispersed into the composite material system, and meanwhile, a composite lubricant can firstly move to the outer side of a material melt and be enriched on the surface layer of the material, so that the lubricating performance of the whole material system can be improved;
(2) The titanate coupling agent in the functional talcum powder master batch can increase the interfacial binding force and compatibility between talcum powder and polypropylene, thereby improving the comprehensive mechanical property of the polypropylene composite material system;
(3) The invention utilizes the interlayer gap characteristics of the regular lamellar structure of high-mesh talcum powder in the functional talcum powder master batch, can adsorb odor micromolecules generated by a curing material in the extrusion production process, can reduce the odor emission performance of a composite material system, and can also utilize the interlayer sliding characteristics of the composite material system to play a synergistic effect with a composite lubricant so as to improve the sticking problem of the material in the injection production process;
(4) The preparation process of the polypropylene composite material with improved sticking, high performance and thinned wall is simple, the production cost is low, and the polypropylene composite material with better comprehensive performance can be prepared.
Detailed Description
The present invention will be described in detail with reference to specific examples. The components in the examples are parts by weight, unless otherwise specified.
The contents of the components contained in the examples and comparative examples of the present invention are shown in Table 1.
Table 1 the contents (mass%) of the main components in examples and comparative examples
The polypropylene in the above examples and comparative examples in Table 1 was a copolymer polypropylene, and was formulated in a 2:1 ratio using EP5075, 5075X, BX3920,3920, and the grades EP5075X were produced by Zhongsha petrochemical industry, the melt flow rates were 60g/10min, and the grades BX3920 were produced by Korea SK company, and the melt flow rates were 100g/10min. The talcum powder is 10000 meshes of talcum powder, and is from Shanghai Yuan Jiang chemical industry Co., ltd, and the elastomer is thermoplastic POE elastomer produced by LG company, and the brand is 168. The high-flow polypropylene, the high-mesh talcum powder and the elastomer in the functional talcum powder master batch are the same as the above; the composite lubricant in the functional talcum powder master batch is compounded by adopting ethylene bis-stearylamide and stearate according to the proportion of 1:1, wherein the ethylene bis-stearylamide is N, N_ethylene bis-stearylamide, sigma aldrich (Shanghai) trade company, and the stearate is magnesium stearate from Shanghai source leaf biotechnology company; the coupling agent in the functional talcum powder master batch is titanate coupling agent, the brand is TC-70, and the functional talcum powder master batch is from Hongsheng fine chemical company; lubricant 1 is N, N_ethylene bis stearamide, and lubricant 2 is magnesium stearate; the antioxidant is 1010 (pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate)/tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168)/DSTP (stearyl thiodipropionate) compound antioxidant according to the mass ratio of 1:2:1. The other auxiliary agents mainly refer to color components, light stabilizers and the like.
The specific implementation of the above embodiment is as follows:
A. preparing functional talcum powder master batch:
adding high-flow polypropylene, an elastomer, high-mesh talcum powder, a composite lubricant and a coupling agent into a high-speed mixer according to weight components, uniformly mixing, transferring into a mixing chamber of an internal mixer for high-speed banburying and mixing, transferring the banburying and mixing block materials into a double-wrist feeding port for feeding, and extruding, air-cooling and granulating by a single-screw extruder to prepare the functional talcum powder master batch. Wherein the temperature of a banburying chamber in the banburying machine is set at 170-190 ℃, the diameter of a single screw is 70mm, the length-diameter ratio is 12, the single screw extruder is divided into three sections, the temperature is controlled, and the temperature from a feeding port to each section of a machine head is 180 ℃, 200 ℃ and 210 ℃ in sequence.
B. The demolding, high-performance and thin-wall polypropylene composite material is improved, and the preparation method thereof is as follows:
(1) Weighing the components according to the mass ratio;
(2) Placing the components such as polypropylene, functional talcum powder master batch, elastomer, antioxidant and other auxiliary agents into a high-speed mixer for high-speed mixing for 5-10min;
(3) Adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, carrying out melt extrusion, bracing, cooling and granulating, and then carrying out material drying treatment to prepare the polypropylene composite material with improved demoulding, high performance and thinned wall, wherein the processing process temperatures of all areas of the double-screw extruder are as follows: a region: 180-205 ℃, 190-205 ℃ in the second region, 210-215 ℃ in the third region, 205-210 ℃ in the fourth region and 190-200 ℃ in the machine head. The whole extrusion process is carried out for about 2 minutes under the pressure of 12-18Mpa, the rotation speed of a main screw is 500-800r/min, the temperature of a water tank is 30-60 ℃, double vacuum pumping is added at two sides of a double screw extruder, the vacuum degree of double vacuum is-0.07 MPa to-0.08 MPa, and a material drying process is adopted for material drying: and (3) storing materials in a tank A, drying materials in a tank B, and cooling the tank C, wherein the tank B is subjected to a material drying process: 130 ℃ 4H.
C. The composite particles prepared as described above were dried in a forced air oven at 80-100 ℃ for 2 hours, and then the dried particles were injection molded on an injection molding machine, followed by performance testing.
D. Basic mechanical property test: the density was measured according to ISO1183-1, the melt index was measured according to ISO1133-1, the temperature was 230 ℃, the load was 2.16kg, the tensile strength was measured according to ISO527-2, the spline size was 170 x 10 x 4mm, the tensile speed was 50mm/min, the flexural modulus was measured according to ISO178, the spline size was 80 x 10 x 4mm, the span was 64mm, the flexural speed was 2mm/min, the notched impact strength of the simple beam was measured according to ISO179-1, the spline size was 80 x 10 x 4mm, and the notch depth was one fifth of the sample width. The odor test of the parts was evaluated according to the PV3900 method, taking 30-mould parts, and placing the cut samples in 1L odor bottles at 80 ℃ by 2H to 60 ℃ for evaluation. The effect of improving the sticking phenomenon of the part was evaluated as follows: the material is molded into a 300-100-1.5 mm template under a specific injection molding process, the template starts to evaluate after being molded into 30 moulds, and the surface sticking effect of the template when the template is demolded can be classified into no sticking phenomenon, slight sticking phenomenon, more sticking phenomenon and serious sticking phenomenon by naked eyes.
Table 2 material property test data in examples and comparative examples
From the data of the examples and comparative examples in the above tables, it can be found that high performance materials meeting the performance requirements of thinned materials with high melt index, high modulus and high toughness can be prepared by selecting suitable polypropylene base materials, high performance fillers and elastomer tougheners. Particularly, the data of the examples 1-7 show that the thinned materials with different specifications can be prepared through reasonable design of the formula, wherein the rigidity and toughness balance performance of the example 7 is optimal, the fluidity of the material is close to 40, and the material can be completely used for preparing ultrathin-wall parts; as can be seen from examples 1-7 and comparative examples 1-4, the thinned polypropylene composite system with the added high-efficiency functional talc master batch has almost no sticking phenomenon, while the composite system prepared by the talc plus auxiliary agent scheme has different degrees of forming. From a further comparison of example 7 with comparative examples 1 to 4, it was found that the addition of the lubricant had a significant improvement in the sticking of the material system; the lubricant is found to be obviously better than a single lubrication system in the improvement of the sticking mode of a material system by adopting a compound mode under the same addition amount, and meanwhile, the improvement of the comparison example 7 and the comparison example 3 show that in the scheme, the embodiment 7 can achieve a small total addition amount when the compound lubricant is selected to be prepared into the functional talcum powder master batch in advance, but the effect of improving the sticking mode is better than that of the comparison example 3; meanwhile, the phenomenon of no sticking to the mold is found to be improved, and the odor of parts is better, firstly, the adsorption solidification function of the interlayer gaps of talcum powder with a regular lamellar structure is selected to play a role in the scheme, and secondly, the phenomenon that after the lubricating property of a material melt is improved in the flowing process, the shearing heat of the material melt in the flowing process is reduced, and the two exert a synergistic effect, so that the odor micromolecule emission of a material system is reduced; in conclusion, the invention adopts the high-efficiency functional talcum powder master batch to replace the traditional modified polypropylene formula to directly prepare the material by using the talcum powder and auxiliary agent in the formula design of the thinned polypropylene composite material, and can prepare the thin-walled polypropylene composite material with improved die bonding, high performance.
Claims (9)
1. A polypropylene composite material with improved die sticking, high performance and thin wall is characterized in that: the adhesive comprises the following raw materials in parts by weight:
polypropylene: 57-75;
functional talcum powder master batch: 14-28;
an elastomer: 8-17;
an antioxidant: 0-1;
other auxiliary agents: 0-3;
the functional talcum powder master batch is prepared from the following components in parts by weight: 10 parts of high-flow polypropylene, 15 parts of elastomer, 71.5 parts of high-mesh talcum powder, 1.5 parts of composite lubricant and 2 parts of coupling agent; the composite lubricant is prepared by compounding ethylene bis-stearylamide and stearate in a ratio of 1:1.
2. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the polypropylene matrix resin adopts one or two mixtures of high-fluidity copolymerized polypropylene, and the melt index is 60g-100g/10min under the condition of 230 ℃ and 2.16 Kg.
3. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the high-flow polypropylene has a melt index of 60-100g/10min at 230 ℃ and 2.16 Kg.
4. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the elastomer is an ethylene and octene copolymer.
5. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the high-mesh talcum powder is 10000-mesh talcum powder and has a regular lamellar structure.
6. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the ethylene bis stearylamide is N, N_ethylene bis stearylamide, and the stearate is one of calcium stearate and magnesium stearate; the coupling agent is titanate coupling agent.
7. An improvement according to claim 1The adhesive-molded, high-performance and thin-walled polypropylene composite material is characterized in that: the elastomer is an ethylene and octene copolymer with a density of 0.86-0.90g/cm 3 The melt index is 0.5-6g/10min.
8. The improved die bonding, high performance, thinned polypropylene composite of claim 1, wherein: the antioxidant is one or more than two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), tri [2, 4-di-tert-butylphenyl ] phosphite ester (antioxidant 168), stearyl thio-dipropionate (antioxidant DSTP), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester (antioxidant 1076); the other auxiliary agent is one or a combination of a plurality of color components, light stabilizer and processing auxiliary agent.
9. The process for preparing a modified, high performance, thin walled polypropylene composite as claimed in any of claims 1 to 8, characterized by the steps of:
A. preparing functional talcum powder master batch:
adding high-flow polypropylene, an elastomer, high-mesh talcum powder, a composite lubricant and a coupling agent into a high-speed mixer according to weight components, uniformly mixing, transferring into a mixing chamber of an internal mixer for high-speed banburying and mixing, transferring the banburying and mixing block materials into a double-wrist feeding port for feeding, extruding, air-cooling and granulating by a single-screw extruder to prepare functional talcum powder master batch; wherein the temperature of a banburying chamber in the banburying machine is set at 170-190 ℃, the diameter of a single screw is 70mm, the length-diameter ratio is 12, the single screw extruder is divided into three sections for controlling the temperature, and the temperatures from a feeding port to each section of a machine head are 180 ℃, 200 ℃ and 210 ℃ in sequence;
B. the demolding, high-performance and thin-wall polypropylene composite material is improved, and the preparation method thereof is as follows:
(1) Weighing the components according to the mass ratio;
(2) Placing polypropylene, functional talcum powder master batch, elastomer, antioxidant and other auxiliary components into a high-speed mixer for high-speed mixing for 5-10min;
(3) Adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, carrying out melt extrusion, bracing, cooling and granulating, and then carrying out material drying treatment to prepare the polypropylene composite material with improved demoulding, high performance and thinned wall, wherein the processing process temperatures of all areas of the double-screw extruder are as follows: a region: 180-205 ℃, 190-205 ℃ in the second region, 210-215 ℃ in the third region, 205-210 ℃ in the fourth region and 190-200 ℃ in the machine head; the time of the whole extrusion process is 2 minutes, the pressure is 12-18Mpa, the rotating speed of a main screw is 500-800r/min, the temperature of a water tank is 30-60 ℃, double vacuum pumping is added at two sides of a double screw extruder, the vacuum degree of the double vacuum is-0.07 MPa to-0.08 MPa, and a material drying process is adopted in material drying treatment: and (3) storing materials in a tank A, drying materials in a tank B, and cooling the tank C, wherein the tank B is subjected to a material drying process: 130 ℃ 4H.
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| CN102604206A (en) * | 2012-02-06 | 2012-07-25 | 金发科技股份有限公司 | Superfine talcum powder-polypropylene filled master batch, preparation method and equipment thereof |
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