CN102295812B - Preparation method of modified microcrystal muscovite/acrylic rubber/PVC composite material - Google Patents
Preparation method of modified microcrystal muscovite/acrylic rubber/PVC composite material Download PDFInfo
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- CN102295812B CN102295812B CN 201110194376 CN201110194376A CN102295812B CN 102295812 B CN102295812 B CN 102295812B CN 201110194376 CN201110194376 CN 201110194376 CN 201110194376 A CN201110194376 A CN 201110194376A CN 102295812 B CN102295812 B CN 102295812B
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Abstract
The invention relates to a method for preparing a modified microcrystal muscovite/acrylic rubber/PVC composite material. According to the invention, modified microcrystal muscovite inorganic rigid particles are adopted as a packing material; acrylic rubber elastic particles are adopted as an impact modifier; PVC (polyvinyl chloride) is adopted as a basis material; and a melt-blending technology is adopted, such that the modified microcrystal muscovite/acrylic rubber/PVC composite material is obtained. The invention belongs to the field of composite materials. The prepared modified microcrystal muscovite/acrylic rubber/PVC composite material has a tensile strength of 63.89 to 68.87MPa, a notched impact strength of 7.84 to 9.40KJ/m<2>, a flexural modulus of 3825 to 4341MPa, a hardness of 85to 86, a vicat softening temperature of 89.6 to 92.9 DEG C, and a glass-transition temperature of 63.5 to 65.4 DEG C. With the method provided by the invention, the mechanical property, the thermal stability and the heat resistance of the composite material are improved; and the aging of the composite material is retarded. The modified microcrystal muscovite/acrylic rubber/PVC composite material provided by the invention can be widely applied in the fields of light industry, mechanics, construction, agriculture, medical treatment, electronics, textile, and aerospace.
Description
Technical field
The present invention relates to take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, the PVC(polyvinyl chloride) be body material, adopt the melt blending technology to prepare the method for modified microcrystal muscovite/acrylic rubber// PVC matrix material, belong to field of compound material.The modified microcrystal muscovite/acrylic rubber/of the present invention's preparation/PVC matrix material has good mechanical property and thermal stability, can be widely used in the fields such as light industry, machinery, building, agricultural, medical treatment, electronics, weaving and aerospace.
Background technology
PVC is one of the world's five large general-purpose plastics, account for about 30 % of synthetic resins total amount, have the characteristics such as nonflammable, corrosion-resistant, insulation, isolation effect be good, its output is only second to polyethylene and occupy the second of world's resin yield, one of the widest plastics variety of Application Areas [Wang Lan, Wang Peizhang, Lu Xiaozhong. macromolecular material [M]. Beijing: the .2009 of China Light Industry Press].But simultaneously PVC belongs to hard brittle material, and its poor toughness, thermotolerance is low and the defective such as poor heat stability has limited further developing and using of it greatly.How effectively to improve the over-all properties of PVC material, exploitation has high tensile, high impact, the good PVC matrix material of thermal stability, widens its Application Areas, is to be badly in need of one of major issue that solves in current PVC investigation of materials.
There are some researches show, adopt inorganic rigid particle (as CaCO
3, SiO
2, Al (OH)
3, MgO, clay etc.) and elastic particle (as MBS, CPE, ABS, ACR etc.) modified polymer material, some excellent properties that not only can keep macromolecular material self, also can effectively improve intensity and the toughness of macromolecular material, give simultaneously macromolecular material good thermotolerance, delay the lax of macromolecular material, [Quan Ying increases the service life, Yang Mingshan, Yan Qing, Deng. the toughness reinforcing reinforced effects [J] of nano redigity particle to hard PVC. Beijing University of Chemical Technology's journal (natural science edition), 2002,29 (6); Xiong Ying, Chen Guangshun, Guo Shaoyun. the research progress of toughening modification of PVC [J]. polyvinyl chloride, 2004, (2); Tian Manhong, Guo Shaoyun. nanometer CaCO
3The power chemistry of filling pvc composite strengthens Research on Toughening [J]. polyvinyl chloride, 2003, (6); Wan Chaoying, Qiao Xiuying opens brave. the structure of Polyvinylchloride/montmorillonite Nanocomposite and mechanical property [J]. and Shanghai Communications University's journal, 2003,37 (5); Pan Mingwang, Zhang Liucheng, Yuan Jinfeng, wait .ACR-g-PVC composite particles structure with to the toughening efficiency [J] of PVC. polymer journal, 2005, (1)].But there are certain difference in dissimilar inorganic rigid particle and elastic particle to the degree that improves the macromolecular material performance.
Microcrystal muscovite is a kind of novel white mica class mineral wealth of finding in area, west, river in recent years, excellent property, and reserves are abundant.Be colourless, canescence, light green, transparent, vitreous luster, cleavage surface is pearliness, and { the 001} cleavage is extremely complete, { 110} and { the 010} cleavage is incomplete; Refractive index Ng=1.598, Nm=1.592, Np=1.564, hardness 2.56, proportion 2.86; Its crystalline particle natural superfine, particle diameter are less than 10 μ m, and general 1 μ m ~ 5 μ m have micron-sized crystal or wafer (being called for short " crystallite "); Main chemical compositions (weight percent) is: SiO
245.7 %, A1
2O
330.51 %, K
2O11.63 %, H
2O4.53 %.Compare with other common silicate mineralss, microcrystal muscovite has high strength, heat-resisting, acid and alkali-resistance, insulation, chemically stable, weathering resistance, antiultraviolet, the excellent properties such as anti-aging; With traditional white mica mineral facies ratio, the characteristic that it has natural fine size, easily grind, chemically reactive is high, it is a kind of high-quality inorganic rigid particle filler, [Lin Jinhui has broad application prospects in the PVC based composites, Wang Ling, Deng Miao, etc. the mineralogical characteristic research [J] of the regional microcrystal muscovite in west, river. Minerals And Rocks, 2005,25 (3); Mao Yuyuan, Hou Liwei. the application [J] of the exploitation of new microcrystal muscovite resource and powder body material thereof. Chinese powder technology, 2002,8 (4)].But the wetting ability due to microcrystal muscovite, make it different from the interfacial property of macromolecular material, consistency is poor, be difficult to Uniform Dispersion in the macromolecular material matrix, directly fill some mechanical properties decrease that often easily causes material, therefore, must carry out surface modification to it, improve its dispersiveness in organic substrate.Coupling agent is present most widely used surface-modifying agent, it is applicable to various organic polymer and inorganic mineral filler compound system [Ma Hongxia, remaining omnipotent, Li Yaocang, etc. the application development of inorganic filler and coupling agent [J] in the PVC modified system. polyvinyl chloride .2005 (9); Xue Rujun, Wu Yucheng. the performance [J] of the mechanism of silane coupling agent modification and modification sericite. silicate journal, 2007,35 (3)].
Acrylic elastomer is the elastic particle with core-shell type structure, stratum nucleare is butyl polyacrylate cross-linked elastomer (PBA), shell is methyl methacrylate (PMMA)-X 4460, have higher shock strength, tensile strength, modulus and heat-drawn wire, and better weather resistance.As the PVC impact modifier, due to the synergistic effect between core-shell, can obviously improve the shock resistance of PVC goods, increase the surface smoothness of goods, and the weather resistance of raising goods [Wang Qingguo. ultra-fine fully vulcanized powder rubber and nanometer inorganic filler compound system thereof the study on the modification [D] to rigid polyvinyl chloride. the .2006 of Beijing University of Chemical Technology; Feng Pengcheng, Yu Jianying. nanometer CaCO
3Impact [J] on CPE/ACR blending toughening PVC mechanical property. polymer material science and engineering .2010,26 (1)].
At present, the method for enhancing toughening PVC material can be divided into: chemical modification and the large class of physically modified two.chemical modification is mainly by molecular designing grafting or flexible (rigidity) segment of copolymerization introducing on the molecular chain of PVC, strengthen toughness reinforcing purpose thereby reach, but be subject to the restriction of the aspects such as economy and technology always, its tempo is [Ratnam C.T. slowly, Kamaruddin S., Sivachalam Y., et al. Radiation crosslinking of rubber phase in poly (vinyl chloride)/epoxidized natural rubber blend:Effect on mechanical properties[J] .Polymer Testing, 2006, 25 (4)], physically modified mainly refers to the melt blending modification of polyvinyl chloride resin and other material (elastic particle, non-resilient particle, inorganic rigid particle/elastic particle are compound), be a kind of strengthen the toughening PVC material simple and convenient, effectively, method cheaply.
Through retrieval, do not find take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, PVC is body material, adopts the melt blending technology to prepare patent application or the bibliographical information of the method for modified microcrystal muscovite/acrylic rubber// PVC matrix material.The objective of the invention is, by introducing modification of microcrystalline white mica inorganic rigid particle to improve the PVC strength of materials, introduce simultaneously the acrylic elastomer elastic particle to improve the PVC toughness of material, the method for a kind of modified microcrystal muscovite/acrylic rubber/that prepares high comprehensive performance/PVC matrix material is provided.
Summary of the invention
The present invention relates to take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, PVC is body material, adopts the melt blending technology to prepare the method for modified microcrystal muscovite/acrylic rubber// PVC matrix material, and following processing step is arranged:
(1) microcrystal muscovite is carried out preheating and drying, 90～110 ℃ of drying temperatures, time of drying 2～4, h, removed microcrystal muscovite surface adsorption water;
(2) take γ-aminopropyl triethoxysilane properties-correcting agent by 1.2 % that account for the dry microcrystal muscovite quality of step (1), and γ-aminopropyl triethoxysilane by volume: the ratio preparation γ-aminopropyl triethoxysilane properties-correcting agent diluent of dehydrated alcohol: water=1:2:1;
(3) adopt the dry method modification technology, to mix in homogenizer with the γ-aminopropyl triethoxysilane properties-correcting agent diluent of preparing by step (2) by the dry microcrystal muscovite of step (1), microcrystal muscovite is carried out surface modification, stirring velocity 25000 r/min, surface modification times 250～350 s, preparation modification of microcrystalline white mica;
(4) will mix according to the ratio of mass ratio 35 ~ 40:3 ~ 9:100:10:4 in modification of microcrystalline white mica and acrylic elastomer, PVC, dioctyl phthalate (DOP) softening agent, the plumbous zinc composite stabilizer of step (3) preparation, put into baking oven and under 80 ℃ of conditions, softening agent is absorbed fully, discharging;
The material that (5) will prepare by step (4) is under 175 ℃ ± 5 ℃ conditions in the roller temperature, adopts mixing 8 ~ 10 min of double roll mill;
(6) on temperature is the semi-automatic pressure forming machine of 185 ± 5 ℃, after material preheating 10 min that will mix by step (5), pressed sizing under 20MPa pressure naturally cools to room temperature after pressurize 3 min, makes modified microcrystal muscovite/acrylic rubber// PVC matrix material.
The molecular formula of the said γ-aminopropyl triethoxysilane of above-mentioned processing step (2) is NH
2CH
2CH
2CH
2Si (OC
2H
5)
3The said acrylic elastomer of processing step (4) is LS-61 type resin, has the core-shell type structure, and stratum nucleare is butyl polyacrylate cross-linked elastomer (PBA), and shell is methyl methacrylate (PMMA)-X 4460.
With above-mentioned processing step, the modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through Resarch on A New Type, and its tensile strength is that 63.89～68.87MPa, notched Izod impact strength are 7.84～9.40 KJ/m
2, modulus in flexure is that 3825～4341Mpa and hardness are 85～86, respectively the raising of purer PVC material 7.07～15.42%, 45.73～74.21%, 24.59～41.40% and 26.87～28.36%, the mechanical property of matrix material has obtained obvious improvement; The modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through the thermal stability test analysis, it is 63.5～65.4 ℃ with second-order transition temperature that its vicat softening temperature is 89.6～92.9 ℃, respectively the raising of purer PVC material 14.3～17.6 ℃ and 7.9～9.8 ℃, improve thermostability and the thermotolerance of matrix material, delayed the aging of matrix material.
The modified microcrystal muscovite/acrylic rubber/of the present invention's preparation/PVC matrix material can be applicable to the fields such as light industry, machinery, building, agricultural, medical treatment, electronics, weaving and aerospace.
Four, embodiment
Following examples further illustrate the present invention, but do not limit the present invention.
Embodiment 1:
Modified microcrystal muscovite/acrylic rubber/of the present invention/PVC composite manufacture method, the method is take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, PVC is body material, adopt the melt blending technology, preparation modified microcrystal muscovite/acrylic rubber// PVC matrix material.Its technological process is: microcrystal muscovite is carried out preheating and drying, and 100 ℃ of drying temperatures, time of drying, 3h, removed microcrystal muscovite surface adsorption water; Take γ-aminopropyl triethoxysilane properties-correcting agent by 1.2 % that account for dry microcrystal muscovite quality, and γ-aminopropyl triethoxysilane by volume: the ratio preparation γ-aminopropyl triethoxysilane properties-correcting agent diluent of dehydrated alcohol: water=1:2:1; Adopt the dry method modification technology, the microcrystal muscovite of drying and the γ-aminopropyl triethoxysilane properties-correcting agent diluent of preparation are mixed in homogenizer, microcrystal muscovite is carried out surface modification, stirring velocity 25000 r/min, surface modification times 270 s, preparation modification of microcrystalline white mica; Modification of microcrystalline white mica and acrylic elastomer, PVC, dioctyl phthalate (DOP) softening agent, the plumbous zinc composite stabilizer of preparation are mixed according to the ratio of mass ratio 35:3:100:10:4, put into baking oven and under 80 ℃ of conditions, softening agent is absorbed fully, discharging; Be under 175 ℃ ± 5 ℃ conditions with the material for preparing in the roller temperature, adopt mixing 8 min of double roll mill; Be that on the semi-automatic pressure forming machine of 185 ± 5 ℃, after material preheating 10 min that mix, pressed sizing under 20MPa pressure naturally cools to room temperature after pressurize 3 min, makes modified microcrystal muscovite/acrylic rubber// PVC matrix material in temperature.
With above-mentioned processing step, the modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through Resarch on A New Type, and its tensile strength is that 68.87MPa, notched Izod impact strength are 7.84 KJ/m
2, modulus in flexure is that 4341Mpa and hardness are 86, respectively the raising of purer PVC material 15.42%, 45.73%, 41.40% and 28.36%, the mechanical property of matrix material has obtained obvious improvement; The modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through the thermal stability test analysis, it is 63.5 ℃ with second-order transition temperature that its vicat softening temperature is 92.9 ℃, respectively the raising of purer PVC material 17.6 ℃ and 7.9 ℃, improve thermostability and the thermotolerance of matrix material, delayed the aging of matrix material.
The modified microcrystal muscovite/acrylic rubber/of the present invention's preparation/PVC matrix material can be applicable to the fields such as light industry, machinery, building, agricultural, medical treatment, electronics, weaving and aerospace.
Embodiment 2:
Modified microcrystal muscovite/acrylic rubber/of the present invention/PVC composite manufacture method, the method is take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, PVC is body material, adopt the melt blending technology, preparation modified microcrystal muscovite/acrylic rubber// PVC matrix material.Its technological process is: microcrystal muscovite is carried out preheating and drying, and 110 ℃ of drying temperatures, time of drying, 2h, removed microcrystal muscovite surface adsorption water; Take γ-aminopropyl triethoxysilane properties-correcting agent by 1.2 % that account for dry microcrystal muscovite quality, and γ-aminopropyl triethoxysilane by volume: the ratio preparation γ-aminopropyl triethoxysilane properties-correcting agent diluent of dehydrated alcohol: water=1:2:1; Adopt the dry method modification technology, the microcrystal muscovite of drying and the γ-aminopropyl triethoxysilane properties-correcting agent diluent of preparation are mixed in homogenizer, microcrystal muscovite is carried out surface modification, stirring velocity 25000 r/min, surface modification times 300 s, preparation modification of microcrystalline white mica; Modification of microcrystalline white mica and acrylic elastomer, PVC, dioctyl phthalate (DOP) softening agent, the plumbous zinc composite stabilizer of preparation are mixed according to the ratio of mass ratio 35:6:100:10:4, put into baking oven and under 80 ℃ of conditions, softening agent is absorbed fully, discharging; Be under 175 ℃ ± 5 ℃ conditions with the material for preparing in the roller temperature, adopt mixing 10 min of double roll mill; Be that on the semi-automatic pressure forming machine of 185 ± 5 ℃, after material preheating 10 min that mix, pressed sizing under 20MPa pressure naturally cools to room temperature after pressurize 3 min, makes modified microcrystal muscovite/acrylic rubber// PVC matrix material in temperature.
With above-mentioned processing step, the modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through Resarch on A New Type, and its tensile strength is that 66.00MPa, notched Izod impact strength are 8.90KJ/m
2, modulus in flexure is that 4133MPa and hardness are 86, respectively the raising of purer PVC material 10.61%, 65.43%, 34.63% and 28.36%, the mechanical property of matrix material has obtained obvious improvement; The modified microcrystal muscovite/acrylic rubber/of preparation/PVC matrix material shows through the thermal stability test analysis, it is 64.1 ℃ with second-order transition temperature that its vicat softening temperature is 91.8 ℃, respectively the raising of purer PVC material 16.5 ℃ and 8.5 ℃, improve thermostability and the thermotolerance of matrix material, delayed the aging of matrix material.
The modified microcrystal muscovite/acrylic rubber/of the present invention's preparation/PVC matrix material can be applicable to the fields such as light industry, machinery, building, agricultural, medical treatment, electronics, weaving and aerospace.
Claims (4)
1. take modification of microcrystalline white mica inorganic rigid particle as filler, the acrylic elastomer elastic particle is impact modifier, the PVC(polyvinyl chloride) be body material, adopt the melt blending technology to prepare the method for modified microcrystal muscovite/acrylic rubber// PVC matrix material, its feature has following processing step:
(1) microcrystal muscovite is carried out preheating and drying, 90～110 ℃ of drying temperatures, time of drying 2～4, h, removed microcrystal muscovite surface adsorption water;
(2) take γ-aminopropyl triethoxysilane properties-correcting agent by 1.2 % that account for the dry microcrystal muscovite quality of step (1), and γ-aminopropyl triethoxysilane by volume: the ratio preparation γ-aminopropyl triethoxysilane properties-correcting agent diluent of dehydrated alcohol: water=1:2:1;
(3) adopt the dry method modification technology, to mix in homogenizer with the γ-aminopropyl triethoxysilane properties-correcting agent diluent of preparing by step (2) by the dry microcrystal muscovite of step (1), microcrystal muscovite is carried out surface modification, stirring velocity 25000 r/min, surface modification times 250～350 s, preparation modification of microcrystalline white mica;
(4) will mix according to the ratio of mass ratio 35 ~ 40:3 ~ 9:100:10:4 in modification of microcrystalline white mica and acrylic elastomer, PVC, dioctyl phthalate (DOP) softening agent, the plumbous zinc composite stabilizer of step (3) preparation, put into baking oven and under 80 ℃ of conditions, softening agent is absorbed fully, discharging;
The material that (5) will prepare by step (4) is under 175 ℃ ± 5 ℃ conditions in the roller temperature, adopts mixing 8 ~ 10 min of double roll mill;
(6) on temperature is the semi-automatic pressure forming machine of 185 ± 5 ℃, after material preheating 10 min that will mix by step (5), pressed sizing under 20MPa pressure naturally cools to room temperature after pressurize 3 min, makes modified microcrystal muscovite/acrylic rubber// PVC matrix material.
2. modified microcrystal muscovite/acrylic rubber/according to claim 1/PVC composite manufacture method, the molecular formula that it is characterized in that said γ-aminopropyl triethoxysilane is NH
2CH
2CH
2CH
2Si (OC
2H
5)
3Said acrylic elastomer is LS-61 type resin, has the core-shell type structure, and stratum nucleare is butyl polyacrylate cross-linked elastomer (PBA), and shell is methyl methacrylate (PMMA)-X 4460.
3. modified microcrystal muscovite/acrylic rubber/according to claim 1/PVC composite manufacture method, the tensile strength that it is characterized in that this modified microcrystal muscovite/acrylic rubber// PVC matrix material is that 63.89～68.87MPa, notched Izod impact strength are 7.84～9.40 KJ/m
2, modulus in flexure is that 3825～4341Mpa and hardness are 85～86.
4. modified microcrystal muscovite/acrylic rubber/according to claim 1/PVC composite manufacture method, the vicat softening temperature that it is characterized in that this modified microcrystal muscovite/acrylic rubber// PVC matrix material are that 89.6～92.9 ℃ and second-order transition temperature are 63.5～65.4 ℃.
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