CN110591223B - High-filling thermoplastic resin composite material and preparation method thereof - Google Patents
High-filling thermoplastic resin composite material and preparation method thereof Download PDFInfo
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a high-filling thermoplastic resin composite material which comprises the following components in parts by weight: 60 parts of thermoplastic resin; 40-540 parts of reinforcing fiber and filler; the reinforcing fiber and the filler are 0.002-0.012 times of polyfunctional group polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group. The highly filled thermoplastic resin composite material has the advantages of excellent hydrolysis resistance and freezing resistance. The invention also provides a preparation method of the high-filling thermoplastic resin composite material, which can improve the production yield of the high-filling thermoplastic resin composite material.
Description
Technical Field
The invention relates to the technical field of novel high-molecular composite materials, in particular to a high-filling thermoplastic resin composite material and a preparation method thereof.
Background
The past examples of the channel protection project show that the damage of the beach or the bottom of the channel protection building is one of the main reasons for the damage of the protection building and the instability of the beach channels. At present, the beach or the foundation of the building is protected from scouring by the protection measures, and the beach or the foundation is maintained to be stable by the self weight of the beach or the foundation protection row body. Under the condition of high water flow, due to the pulsating nature of the water flow and the like, the situation that the edge of the row body or the local brushing between the protection bodies finally forms serious damage is more common.
Chinese patent CN 103122619B, CN 103122620B, CN 103122621B, CN 103122623B, CN 103122624B, CN 103122625B, CN 103103961B etc. provides a protection hook disjunctor that the component itself can realize hooking separately under the state of throwing scattered, and it can effectively improve submarine water flow structure, forms better energy dissipation scour protection effect in guarding the district, has better stability, durability and economic nature and makes things convenient for the engineering construction.
Therefore, the development of the polymer composite material suitable for the hook connecting body has great economic value. However, the high-density and high-strength high-filling polypropylene composite material has too high filler, and the compatibility among the polypropylene, the filler and the reinforcing fiber can be solved by adding the compatilizer, so that the production yield and the mechanical property are improved, and the density is improved. Chinese patent 201310683859.2 discloses a method for preparing a multifunctional plastic additive, which can improve compatibility, processability, fluidity and the like, but does not describe that hydrolysis resistance and freezing resistance can be improved.
However, the hook connecting body is mainly used for channel protection and flood control, and has high requirements on mechanical properties, hydrolysis resistance and freezing resistance. Generally, for improving hydrolysis resistance, 201610607013.4 discloses a polypropylene composite material, which is added with fluoropolymer to improve surface properties and prevent water from penetrating, so as to improve hydrolysis resistance; 201210574617.5 discloses a polypropylene composite material, wherein the addition of heat stabilizer can inhibit the degradation generated in the processing process and prevent the hot water from extracting the antioxidant system, thereby effectively improving the aging resistance of the kettle material. For improving the freezing resistance, it is known to modify the thermoplastic resin (such as epoxy resin grafted polypropylene), add cold resistance agent (dioctyl adipate or dioctyl sebacate), add organic hydrazide nucleating agent, and the like. However, the above methods can only solve one of the problems, and the hydrolysis resistance and the freezing resistance are difficult to be simultaneously improved by adding one additive.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a high-filling thermoplastic resin composite material which has the advantages of excellent hydrolysis resistance and freezing resistance.
The invention also aims to provide a preparation method of the high-filling thermoplastic resin composite material, which effectively improves the production yield.
The invention is realized by the following technical scheme:
a highly filled thermoplastic resin composite material comprises the following components in parts by weight:
60 parts of thermoplastic resin;
40-540 parts of reinforcing fibers and fillers;
the reinforcing fiber and the filler are 0.002-0.012 times of polyfunctional group polymer containing two or more than two active groups of ether group, imide group, ester group, amino group and siloxy group.
Preferably, the composition comprises the following components in parts by weight:
60 parts of thermoplastic resin;
90-540 parts of reinforcing fibers and fillers;
the reinforcing fiber and the filler are 0.004-0.010 times of the dosage of the polyfunctional group polymer containing two or more than two active groups of ether group, imide group, ester group, amino group and siloxy group.
The multifunctional group polymer containing two or more than two active groups of ether group, imino group, ester group, amino group and siloxy group is at least one selected from acrylate-polyurethane-siloxane polymer, acrylate-siloxane polymer and amino-terminated hyperbranched polyamide;
the compounds are generally added as compatilizers, flow aids, dispersants or lubricants, mainly characterized by processability and improved mechanical properties. In experiments, the invention discovers that when high filling is carried out, the addition of a small amount of the auxiliary agent can increase the freezing resistance and hydrolysis resistance of the high-filling thermoplastic resin composite material, improve the stability of the hook-and-link body made of the high-filling thermoplastic resin composite material in a river with complex water conditions and prolong the service life.
Preferably, the multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group is at least one selected from acrylate-polyurethane-siloxane polymer and acrylate-siloxane polymer.
The preparation method of the acrylate-polyurethane-siloxane polymer can be that 60-80 parts of aliphatic acrylate polyurethane oligomer, 5-15 parts of acrylic monomer and 0.1-5 parts of vinyl silicone oil are polymerized at the temperature of 162-170 ℃ in the presence of a free radical initiator, and the reaction process is controlled by the reaction time, the reaction temperature and the adding amount of the initiator. The acrylate-siloxane polymer can be prepared by the above-mentioned method, and the polymerization reaction can be carried out using an acrylate oligomer, an acrylic monomer, and a vinyl silicone oil as base materials.
The preparation method of the amino-terminated hyperbranched polyamide comprises the following steps: dripping a methanol solution of an acrylate compound monomer into a methanol solution of a polyaminoamine monomer (ammonia, ethylenediamine, hexamethylenediamine, diethylenetriamine) in an ice bath to obtain a mixed solution; reacting for 30-55h at room temperature under the protection of inert gas, and distilling under reduced pressure at 55-65 ℃ to obtain a crude product; the obtained crude product reacts for 2-7h at the temperature of 110-160 ℃ to obtain the amino-terminated hyperbranched polyamide product.
In order to improve the compatibility of the reinforcing fibers and the filler with the thermoplastic resin matrix, the thermoplastic resin matrix also comprises a compatilizer with the dosage of 0.02 to 0.2 times of the reinforcing fibers and the filler in parts by weight; the compatilizer is selected from maleic anhydride grafted polyolefin; the maleic anhydride grafted polyolefin is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene.
The compatilizer is added in the invention, so that the compatibility of the reinforced fiber and the filler with the thermoplastic resin matrix is improved, and the processing performance is also improved.
The reinforcing fiber is selected from glass fiber; the retention length of the glass fiber in the high-filling thermoplastic resin composite material is 0.2-0.6 mm.
The filler is selected from inorganic mineral fillers; the inorganic mineral filler is at least one selected from calcium carbonate, barium sulfate, calcium sulfate, talcum powder, quartz powder and wollastonite.
The thermoplastic resin is at least one selected from polypropylene and polyethylene.
In order to improve the toughness of the high-filling thermoplastic resin composite material, 0-24 parts of a toughening agent is also included in parts by weight; the toughening agent is selected from a copolymer of polyethylene and alpha-olefin containing 2-10 carbon atoms or a maleic anhydride graft of the copolymer of polyethylene and alpha-olefin containing 2-10 carbon atoms; 0.2 to 8 weight portions of at least one of weather resisting agent, antioxidant and processing aid.
The invention creates a preparation method of a highly filled thermoplastic resin composite material by a three-section type side feeding method, which comprises the following steps:
step 1: weighing the raw materials in parts by weight;
step 2: mixing a thermoplastic resin, a compatilizer and a multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group in a mixer for 3-8 minutes to obtain a mixture, and metering the mixture according to the ratio of length to diameter of 48: 1, a twin-screw extruder with a 12-zone barrel, wherein the filler accounting for 40-60% of the weight ratio of the total filler is metered from the main feed inlet of the twin-screw extruder;
and 3, step 3: and adding the rest of the filler from a feeding port at the 4 th-6 th zone side of the double-screw extruder, adding the reinforcing fiber from a feeding port at the 8 th-9 th zone side of the double-screw extruder, and extruding and molding to obtain the high-filling thermoplastic resin composite material.
The present invention is a highly filled thermoplastic resin composite material which is liable to cause uneven mixing of components if produced by a conventional one-side-feed production method and to break easily during production, and which is liable to cause poor properties due to uneven mixing. The preparation process is a three-section type side feeding method, can better mix all components, improve the retention length of the glass fiber in a product, reduce the phenomena of strip breakage and the like in the production process, and improve the production qualification rate and the production efficiency.
The invention has the following beneficial effects:
the high-filling thermoplastic resin composite material has about 40-90% of filling ratio (preferably 60-90% of filling ratio), and has the advantages of excellent hydrolysis resistance and freezing resistance by adding the multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and silicon-oxygen group; furthermore, the preparation method can effectively improve the production qualification rate.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The invention uses the following raw materials in part, but the invention is not limited by the following raw materials:
the multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group is referred to as multifunctional polymer.
Polypropylene: the brand number N-Z30S, the Branch of Michelson of China petrochemical company Limited;
polyethylene: high density polyethylene with density of 0.95g/cm3；
Barium sulfate: a filler;
calcium carbonate: a filler;
glass fiber: a reinforcing fiber;
a toughening agent: copolymers of ethylene and octene, such as the dow chemical ENGAGE 8150;
a compatilizer: maleic anhydride grafted polypropylene, such as BONDYRAM 1001CN from Polyram;
substance A: an acrylate-urethane-siloxane oligomer, self-made (formula is 65 parts of aliphatic acrylate urethane oligomer, 11 parts of acrylic monomer, and 1.8 parts of vinyl silicone oil);
substance B: amino-terminated hyperbranched polyamide which is prepared by self (the formula is 14 parts by weight of ethylenediamine and 50 parts by weight of methyl acrylate);
antioxidant, 1:1 mixture of hindered phenol main antioxidant and phosphite ester auxiliary antioxidant, main antioxidant: basf Irganox 1010, secondary antioxidant: basf Irganox 168;
weather resisting agent: 1:1 mixture of hindered amine light stabilizer and ultraviolet absorber, hindered amine: basf CHIMASSORB 944, ultraviolet absorber Lianlong UV-531;
preparation of highly filled thermoplastic resin compositions of examples 1-14 and comparative examples: weighing the raw materials in parts by weight; stirring and mixing polypropylene, a compatilizer, a toughening agent, a polyfunctional group polymer, a weather resistant agent and an antioxidant in a mixer for 3-8 minutes to obtain a mixture, wherein the length-diameter ratio of the mixture is 48: 1, a twin-screw extruder with a 12-zone barrel, wherein the filler accounting for 40-60% of the weight ratio of the total filler is metered from the main feed inlet of the twin-screw extruder; and adding the rest filling agent from a feeding port at the 4 th-6 th area side of the double-screw extruder, adding the reinforcing fiber from a feeding port at the 8 th-9 th area side of the double-screw extruder, and extruding and molding to obtain the high-filling polypropylene composite material.
The method of making the highly filled thermoplastic resin composite of example 15: weighing the raw materials in parts by weight; stirring and mixing polypropylene, a filler, a compatilizer, a toughening agent, a polyfunctional group polymer, a weather-resistant agent and an antioxidant in a mixer for 3-8 minutes to obtain a mixture, wherein the length-diameter ratio of the mixture is 48: 1, adding a main feeding port of a double-screw extruder with a 12-zone screw barrel; and adding the reinforced fiber from a feeding port at the 8 th-9 th zone side of the double-screw extruder, and extruding and molding to obtain the high-filling polypropylene composite material.
The performance test method comprises the following steps:
(1) and (3) hydrolysis resistance testing: after being taken out, standard sample bars made of the highly filled thermoplastic resin composite materials of the examples and the comparative examples are soaked in hot water at 95 ℃ for 2500 hours, and the retention rates of the tensile strength, the bending strength and the notched izod impact strength are tested, wherein the retention rate of the tensile strength is = tensile strength after hydrolysis resistance test divided by tensile strength before hydrolysis resistance test multiplied by 100%, the retention rate of the bending strength is = bending strength after hydrolysis resistance test divided by bending strength before hydrolysis resistance test multiplied by 100%, the retention rate of the notched izod impact strength is = notched izod impact strength after hydrolysis resistance test divided by notched izod impact strength before hydrolysis resistance test multiplied by 100%, and finally the total retention rate is calculated as = (tensile strength retention rate + bending strength retention rate + notched izod impact strength retention rate) = 3.
(2) Freezing resistance performance: standard bars made of the highly filled thermoplastic resin composite materials of examples and comparative examples were frozen in a freezer at-10 ℃ for 24 hours, and the retention rates of the izod unnotched impact strength and the izod notched impact strength at-10 ℃ were measured, the retention rate of the izod unnotched impact strength = the izod unnotched impact strength after freezing ÷ the izod unnotched impact strength before freezing × 100%, the retention rate of the izod notched impact strength = the izod notched impact strength after freezing ÷ the izod notched impact strength before freezing × 100%, and finally the total retention rate = (the retention rate of the izod unnotched impact strength + the retention rate of the izod notched impact strength) ÷ 2 was calculated.
(3) The product percent of pass: the weight of the qualified product accounts for the weight ratio of the total input raw materials.
Table 1: examples the proportions (parts by weight) of the components and the results of the performance tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Polypropylene | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| Polyethylene | - | - | - | - | - | - | - |
| Calcium carbonate | 20 | 45 | 90 | 180 | 270 | - | 90 |
| Barium sulfate | - | - | - | - | - | 45 | - |
| Glass fiber | 20 | 45 | 90 | 180 | 270 | 45 | 90 |
| Toughening agent | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Compatilizer | 2 | 4.5 | 9 | 18 | 27 | 4.5 | 3.6 |
| Substance A | 0.2 | 0.45 | 0.9 | 1.8 | 2.7 | 0.45 | 0.36 |
| Substance B | - | - | - | - | - | - | - |
| Antioxidant agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Weather-resistant agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Total retention of hydrolysis resistance% | 92 | 92 | 92 | 94 | 92 | 92 | 90 |
| Overall retention of freeze resistance,% | 93 | 93 | 94 | 94 | 92 | 93 | 92 |
| Percent of pass of the product% | 98.6 | 99.1 | 99.1 | 98.8 | 98.6 | 99.1 | 98.0 |
TABLE 1
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | |
| Polypropylene | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| Polyethylene | - | - | - | - | - | 3 | - | - |
| Calcium carbonate | 90 | 90 | 90 | 90 | 240 | 45 | 20 | 180 |
| Barium sulfate | - | - | - | - | - | - | - | - |
| Glass fiber | 90 | 90 | 90 | 240 | 90 | 45 | 20 | 180 |
| Toughening agent | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Compatilizer | 5.4 | 32.4 | 36 | 16.5 | 16.5 | 4.5 | 2 | 18 |
| Substance A | 0.72 | 1.8 | 2.16 | 1.65 | 1.65 | 0.45 | - | 1.8 |
| Substance B | - | - | - | - | - | - | 0.2 | - |
| Antioxidant agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Weather-resistant agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Total retention of hydrolysis resistance% | 91 | 92 | 91 | 92 | 90 | 91 | 89 | 90 |
| Overall retention of freeze resistance,% | 93 | 91 | 92 | 93 | 93 | 93 | 90 | 91 |
| Percent of pass of the product% | 99.2 | 99.1 | 98.8 | 98.6 | 98.7 | 99.4 | 97.5 | 95.5 |
Table 2: comparative example the proportions (parts by weight) of the components and the results of the performance tests
| Comparative example 1 | Comparative example 2 | Comparison ofExample 3 | Comparative example 4 | |
| Polypropylene | 60 | 60 | 60 | 60 |
| Calcium carbonate | 45 | 180 | 45 | 45 |
| Glass fiber | 45 | 180 | 45 | 45 |
| Toughening agent | 4 | 24 | 4 | 4 |
| Compatilizer | 4.5 | 18 | 0.9 | 4.5 |
| Substance A | - | - | 1.20 | 0.09 |
| Antioxidant agent | 1 | 1 | 1 | 1 |
| Weather-resistant agent | 1 | 1 | 1 | 1 |
| Total retention of hydrolysis resistance% | 81 | 68 | 80 | 85 |
| Overall retention of freeze resistance,% | 65 | 59 | 78 | 81 |
| Percent of pass of the product% | 82 | 77 | 87 | 84 |
As can be seen from examples 3/7-10, the preferable range of the amount of the polyfunctional polymer is that the hydrolysis resistance and the freezing resistance are good, and when the amount of the polyfunctional polymer exceeds 0.010 times of the total amount of the reinforcing fiber and the filler, the hydrolysis resistance and the freezing resistance are not increased any more, so that the amount of the polyfunctional polymer is preferably in the range of 0.004-0.010 times of the amount of the reinforcing fiber and the filler.
From examples 4 and 15, it can be seen that the highly filled polypropylene composite material prepared by the 3-stage side-feeding method of the present invention has high product yield, and hydrolysis resistance and freezing resistance are better than those of the conventional methods.
It can be seen from examples 1 and 14 that the oligomer of acrylate-urethane-siloxane is better in both hydrolysis resistance and freeze resistance than the amino-terminated hyperbranched polyamide.
Claims (7)
1. The highly filled thermoplastic resin composite material is characterized by comprising the following components in parts by weight:
60 parts of thermoplastic resin;
reinforcing fiber and filler 330 and 540 parts;
a polyfunctional group polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group, wherein the dosage of the reinforcing fiber and the filler is 0.004-0.010 times;
the multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group is at least one selected from acrylate-polyurethane-siloxane polymer and acrylate-siloxane polymer.
2. The highly filled thermoplastic resin composite material as claimed in claim 1, further comprising a compatibilizer in an amount of 0.02 to 0.2 times by weight as much as the reinforcing fiber and the filler; the compatilizer is selected from maleic anhydride grafted polyolefin; the maleic anhydride grafted polyolefin is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene.
3. The highly filled thermoplastic resin composite as claimed in claim 1, wherein said reinforcing fibers are selected from the group consisting of glass fibers; the retention length of the glass fiber in the high-filling thermoplastic resin composite material is 0.2-0.6 mm.
4. The highly filled thermoplastic resin composite as claimed in claim 1, wherein said filler is selected from the group consisting of inorganic mineral fillers; the inorganic mineral filler is at least one selected from calcium carbonate, barium sulfate, calcium sulfate, talcum powder, quartz powder and wollastonite.
5. The highly filled thermoplastic resin composite as claimed in claim 1, wherein said thermoplastic resin is at least one selected from the group consisting of polypropylene and polyethylene.
6. The highly filled thermoplastic resin composite as claimed in claim 1, further comprising 0 to 24 parts by weight of a toughening agent; the toughening agent is selected from a copolymer of polyethylene and alpha-olefin containing 2-10 carbon atoms or a maleic anhydride graft of the copolymer of polyethylene and alpha-olefin containing 2-10 carbon atoms; 0.2 to 8 weight portions of at least one of weather resisting agent, antioxidant and processing aid.
7. The method for preparing a highly filled thermoplastic resin composite material as claimed in claim 2, comprising the steps of:
step 1: weighing the raw materials in parts by weight;
step 2: mixing a thermoplastic resin, a compatilizer and a multifunctional polymer containing two or more active groups of ether group, imide group, ester group, amino group and siloxy group in a mixer for 3-8 minutes to obtain a mixture, and metering the mixture according to the ratio of length to diameter of 48: 1, a twin-screw extruder with a 12-zone barrel, wherein the filler accounting for 40-60% of the weight ratio of the total filler is metered from the main feed inlet of the twin-screw extruder;
and 3, step 3: and adding the rest of the filler from a feeding port at the 4 th-6 th zone side of the double-screw extruder, adding the reinforcing fiber from a feeding port at the 8 th-9 th zone side of the double-screw extruder, and extruding and molding to obtain the high-filling thermoplastic resin composite material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910743078.5A CN110591223B (en) | 2019-08-13 | 2019-08-13 | High-filling thermoplastic resin composite material and preparation method thereof |
| PCT/CN2020/103918 WO2021027523A1 (en) | 2019-08-13 | 2020-07-24 | High filling thermoplastic resin composite material and preparation method therefor |
Applications Claiming Priority (1)
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| CN110591223B (en) * | 2019-08-13 | 2022-01-21 | 金发科技股份有限公司 | High-filling thermoplastic resin composite material and preparation method thereof |
| CN111363237A (en) * | 2020-03-02 | 2020-07-03 | 上海大学 | Hydrolysis-resistant polypropylene composite material |
| CN113462150B (en) * | 2021-06-28 | 2023-05-09 | 中广核瑞胜发（厦门）新材料有限公司 | Flame-retardant nylon composite material and preparation method thereof |
| CN113717460A (en) * | 2021-07-22 | 2021-11-30 | 广东金发科技有限公司 | High-surface-hydrophilicity polypropylene composite material and preparation method and application thereof |
| CN113913012A (en) * | 2021-11-18 | 2022-01-11 | 金晶 | Modified thermoplastic composition and application thereof |
| CN114230929A (en) * | 2022-01-18 | 2022-03-25 | 烟台恒大聚合体有限公司 | Composite material for manufacturing plastic bullet and preparation method thereof |
| CN114591587B (en) * | 2022-02-25 | 2023-09-05 | 成都金发科技新材料有限公司 | Polystyrene composite material and preparation method thereof |
| CN115197550B (en) * | 2022-07-20 | 2024-04-02 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
| CN115895209A (en) * | 2022-11-24 | 2023-04-04 | 广州华新科智造技术有限公司 | Calcium carbonate master batch and preparation method and application thereof |
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