CN115895295B - Preparation method of special titanium dioxide pigment for glass fiber reinforced nylon - Google Patents
Preparation method of special titanium dioxide pigment for glass fiber reinforced nylon Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 86
- 239000003365 glass fiber Substances 0.000 title claims abstract description 53
- 239000000049 pigment Substances 0.000 title claims abstract description 38
- 239000004677 Nylon Substances 0.000 title claims abstract description 36
- 229920001778 nylon Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 163
- 239000000047 product Substances 0.000 claims abstract description 63
- 239000002002 slurry Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000004033 plastic Substances 0.000 claims abstract description 18
- 229920003023 plastic Polymers 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 98
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 239000011701 zinc Substances 0.000 claims description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 11
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000004537 pulping Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 229910052984 zinc sulfide Inorganic materials 0.000 description 15
- 239000005083 Zinc sulfide Substances 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 14
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- -1 zinc sulfide modified titanium dioxide Chemical class 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of special titanium dioxide pigment for glass fiber reinforced nylon comprises pulping rutile type titanium dioxide primary product, heating to 70-80 deg.C, and maintaining the temperature in the whole coating process; regulating the pH value of the titanium dioxide slurry to 4-5.4 by using inorganic acid or inorganic alkali solution; adding water-soluble zinc salt solution and water-soluble organic sulfide solution in a certain time, simultaneously using inorganic acid or inorganic alkali solution to maintain pH value at 4-5.4, curing; and then washing until the conductivity of the filter cake is more than 15000 Ω & cm, and then drying and steam-powder treatment are carried out to obtain the special titanium dioxide pigment for the glass fiber reinforced modified plastic. The advantages are that: the process is simple and the operation is easy; the special titanium dioxide pigment for preparing glass fiber reinforced nylon is used in glass fiber reinforced modified plastics, so that the material performance can be improved, and meanwhile, the whiteness of a product can be improved.
Description
Technical Field
The invention relates to a preparation method of a special titanium dioxide pigment for glass fiber reinforced nylon.
Background
Titanium dioxide, also known as titanium dioxide, has high refractive index, high decolorizing power and high hiding power, is the most widely applied white pigment, and is widely applied to industrial production of paint, plastics, paper making, rubber, chemical fiber and the like. Glass fiber reinforced nylon is a composite material with glass fiber as a reinforcing material and nylon resin as a matrix material; compared with nylon, the mechanical strength, rigidity and heat resistance of the glass fiber reinforced plastic are greatly improved, the strength is equivalent to steel, and the glass fiber reinforced plastic has corrosion resistance, electrical insulation and heat resistance. Glass fiber reinforced modified nylon products are widely applied, and particularly, the application in automobiles is gradually increased; besides the automobile industry, the high-precision linear expansion coefficient is small and the electrical performance is good, so the high-precision linear expansion coefficient is widely used in the aspects of electrical and electronic and information technology, and is mainly used for manufacturing office equipment chassis and brackets, instrument covers, junction boxes, switch shells, television rear covers, tuners, fan blades and the like. With the development of wireless technology, currently, various manufacturers are popularizing dual-frequency products of WIFI6 level, namely 5G and 2.4G can receive and transmit signals at the same time; the WIFI6 technology has the advantages that the information interaction quantity of the routing product is greatly improved, and higher requirements are put on heat dissipation of the product. In the aspect of materials, on one hand, a base material with better heat conductivity is selected, and on the other hand, more importantly, the inorganic matters with more components are required to be filled to form better heat conduction network filler, so that the mechanical property of a material system is wholly reduced; therefore, glass fiber reinforced nylon is an ideal material for WIFI6 grade products. For the aesthetic and significance of the product, the design of most manufacturers of the WIFI 6-level product is white. If the glass fiber reinforced nylon product is made white, titanium pigment cannot be used generally, and ZnS is generally used as a white pigment of the glass fiber reinforced nylon. Because the Mohs hardness of the common rutile titanium dioxide is 6.5-7.0 and the hardness of the glass fiber is 5.5-6.0, the common rutile titanium dioxide is used in glass fiber reinforced nylon to ensure that the product has excellent whiteness, but the common rutile titanium dioxide can cut off the abrasion of long glass fiber in glass fiber reinforced nylon resin due to the high hardness, so that the glass fiber is shortened to cause the glass fiber reinforced nylon product to lose high strength and high modulus performance; in addition, titanium dioxide is added into the glass fiber reinforced modified nylon product, the titanium dioxide is easy to reduce the crystallization temperature of nylon, so that the nylon is crystallized on the surface of the titanium dioxide, the quantity of the nylon crystallized on the glass fiber is reduced, and the strength of the product is greatly reduced. Therefore, zinc sulfide is usually used instead of titanium dioxide in the glass fiber reinforced nylon resin system at present, but the whiteness of a product made of zinc sulfide and the whiteness of a product made of titanium dioxide are still different.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a special titanium dioxide pigment for glass fiber reinforced nylon, which has simple process and easy operation; the special titanium dioxide pigment for preparing glass fiber reinforced nylon can be used in glass fiber reinforced modified plastics to improve material performance and improve whiteness of products.
A preparation method of a special titanium dioxide pigment for glass fiber reinforced nylon comprises the following specific steps:
(1) Beating the rutile type titanium dioxide primary product to obtain titanium dioxide slurry, heating to 70-80 ℃, and maintaining the temperature in the whole coating process;
(2) Regulating the pH value of the titanium dioxide slurry to 4-5.4 by using inorganic acid or inorganic alkali solution; adding water-soluble zinc salt solution and water-soluble organic sulfide solution in a certain time, wherein the addition amount of the water-soluble zinc salt solution is Zn accounting for TiO 2 5-10% by weight, wherein the molar ratio of S in the water-soluble organic sulfide solution to Zn in the water-soluble zinc salt solution is 1.5:1-2:1; and simultaneously, inorganic acid or inorganic alkali solution is used for keeping the pH value at 4-5.4, curing for 60-120 min;
(3) Washing the cured slurry obtained in the step (2) with deionized water at 70-80 ℃ until the conductivity of a filter cake is more than 15000 Ω & cm, drying and steam-powder treatment, and adding TiO in the steam-powder process 2 The weight percent of the silane coupling agent is 2 to 5 percent, and the special titanium dioxide pigment for the glass fiber reinforced modified plastic is prepared.
Further, the silane coupling agent in the step (3) is at least one of octyl triethoxysilane and amyl triethoxysilane.
Further, the water-soluble organic sulfide solution in the step (2) is thiourea solution.
Further, the water-soluble zinc salt solution is at least one of zinc nitrate solution, zinc sulfate solution, zinc chloride solution and zinc acetate solution.
Further, the concentration of the water-soluble zinc salt solution is 20g/L to 100g/L calculated by Zn.
Further, the concentration of the water-soluble organic sulfide solution is 30g/L to 50g/L in terms of S.
Further, the time for adding the water-soluble zinc salt solution and the water-soluble organic sulfide solution is 3 to 4 hours.
Further, in the step (2), the inorganic alkali solution is at least one of sodium hydroxide solution and potassium hydroxide solution, and the mass concentration of the inorganic alkali solution is 20%.
Further, the inorganic acid solution in the step (2) is at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution and phosphoric acid solution, and the mass concentration of the inorganic acid solution is 20%.
Further, the rutile titanium dioxide primary product is a chloride process rutile titanium dioxide primary product.
Further, the concentration of the titanium dioxide slurry is 20% -25%.
Compared with the prior art, the invention has the beneficial effects that:
(1) Under the acidic condition of taking a water-soluble zinc salt solution and a water-soluble organic sulfide solution as raw materials, the uniform and compact zinc sulfide coating layer is easy to coat on the surface of titanium dioxide, the coating layer not only effectively compensates photochemical points of the titanium dioxide product and ensures excellent weather resistance of the product, but also can effectively reduce the hardness of the titanium dioxide product, reduce the crystallization quantity of resin on the surface of titanium dioxide and reduce abrasion and cutting of long glass fibers in glass fiber reinforced modified plastic resin; the crystallization speed of the resin is also accelerated, the crystallinity of the resin is improved, and the formation of the serial crystals in the composite material is facilitated, so that the improvement of the mechanical property of the composite material is facilitated.
(2) The silane coupling agent octyl triethoxysilane and/or amyl triethoxysilane coated in the steam powder process can effectively improve the compatibility and the dispersibility of the titanium pigment product in the glass fiber reinforced modified plastic, and reduce the influence on the material performance of the product caused by adding titanium pigment. The product coated with the titanium dioxide surface through the zinc sulfide and the silane coupling agent can not only improve the material performance of the glass fiber reinforced modified plastic, but also improve the whiteness of the product.
In conclusion, the titanium dioxide pigment prepared by the invention has high whiteness, excellent weather resistance and material performance, can be widely used for glass fiber reinforced modified nylon plastic products with high quality requirements, such as junction boxes, switch shells, WIFI 6-level dual-frequency wireless AP (Access Point) and the like, and fills the blank in the field.
Drawings
FIG. 1 is a transmission electron micrograph of titanium dioxide pigment prepared in example 3 and comparative example 4 of the present invention;
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the application scope of the present invention is not limited to the examples, and various substitutions and modifications can be made without departing from the technical spirit of the present invention, and the scope of the present invention is defined by the appended claims.
Example 1
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 20 percent, the temperature is raised to 70 ℃, and the temperature is maintained in the whole coating process.
1.2 quality of useHydrochloric acid with the concentration of 20% or sodium hydroxide with the mass concentration of 20% is used for adjusting the pH value of the slurry to 4; the thiourea solution and the 5% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3 hours 2 Weight) the molar ratio of S in the thiourea solution to Zn in the zinc nitrate solution is 2:1; wherein the concentration of the zinc nitrate solution is 20g/L calculated by Zn, the concentration of the thiourine solution is 50g/L calculated by S, and meanwhile, the pH value is controlled to be 4 by hydrochloric acid with the mass concentration of 20 percent, and the curing is carried out for 120min.
1.3 washing the cured slurry in the step (2) with 70 ℃ ion water until the electric conductivity of the filter cake is 16500 Ω & cm, drying and steam-pulverizing, adding 2% octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam-pulverizing process 2 Weight) to prepare the special titanium dioxide pigment for glass fiber reinforced modified plastics.
Example 2
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 25 percent, the temperature is raised to 80 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5.4 by using sulfuric acid with the mass concentration of 20% or potassium hydroxide solution with the mass concentration of 20%; a thiourea solution and a 10% zinc sulfate solution (the addition amount of the zinc sulfate solution is based on the weight of Zn accounting for TiO 2) were added within 4 hours, and the molar ratio of S in the thiourea solution to Zn in the zinc sulfate solution was 1.5:1, wherein the concentration of the zinc nitrate solution is 100g/L in terms of Zn, the concentration of the thiourine solution is 30g/L in terms of S, and simultaneously, the pH value is controlled to be 5.4 by using potassium hydroxide with the mass concentration of 20 percent, and the curing is carried out for 60 minutes.
1.3 washing the cured slurry in the step (2) with deionized water at 80 ℃ until the conductivity of the filter cake is 15500 Ω & cm, drying and steam-powder treatment, and adding 5% of amyl triethoxysilane coupling agent (the silane coupling agent accounts for TiO) in the steam-powder process 2 Weight) to prepare the special titanium dioxide pigment for glass fiber reinforced modified plastics.
Example 3
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90 minutes.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of the filter cake is 18000 Ω & cm, drying and steam-pulverizing, and adding 4% of octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam-pulverizing process 2 Weight) to prepare the special titanium dioxide pigment for glass fiber reinforced modified plastics.
Comparative example 1
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, the pH value of the slurry is regulated to 5 by sodium hydroxide solution in the whole curing process, and the slurry is cured for 90 minutes.
1.2 washing the cured slurry with deionized water at 75deg.C until the electric conductivity of the filter cake is 18000 Ω & cm, drying, and pulverizing, wherein 4% octyl triethoxysilane coupling agent (with silane coupling agent accounting for TiO) is added in the pulverizing process 2 Weight) to produce titanium dioxide pigment.
Comparative example 2
Comparative example 2 is the same as example 3 except that in step 1.3: adding 4% octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam powder process 2 Weight).
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90 minutes.
1.3 washing the cured slurry obtained in the step (2) with deionized water at 75 ℃ until the conductivity of a filter cake is 18000 Ω & cm, and then drying and steam-powder treatment to obtain the zinc sulfide modified titanium dioxide pigment.
Comparative example 3
The same as in comparative example 1, except that in step 1.2: adding 4% octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam powder process 2 Weight).
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, the pH value of the slurry is regulated to 5 by sodium hydroxide solution in the whole curing process, and the slurry is cured for 90 minutes.
1.2 washing the cured slurry with deionized water at 75 ℃ until the electric conductivity of a filter cake is 18000 Ω & cm, and then drying and steam-powder treatment to obtain the titanium dioxide pigment.
Comparative example 4
As in example 3, except in step 1.2: adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; sodium sulfide solution and 8% zinc nitrate solution (zinc nitrate solution was added in such an amount that Zn accounted for TiO) were added over 3.5 hours 2 Weight percent) of S in the sodium sulfide solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the sodium sulfide solution is 40g/L based on S, meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the mixture is cured to be 90min。
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; sodium sulfide solution and 8% zinc nitrate solution (zinc nitrate solution was added in such an amount that Zn accounted for TiO) were added over 3.5 hours 2 Weight) of S in the sodium sulfide solution and Zn in the zinc nitrate solution, wherein the molar ratio of the S in the sodium sulfide solution to the Zn in the zinc nitrate solution is 1.8:1, the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the sodium sulfide solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 5 by using 20% hydrochloric acid with mass concentration or 20% sodium hydroxide solution with mass concentration, and the curing is carried out for 90min.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of the filter cake is 18000 Ω & cm, drying and steam-pulverizing, and adding 4% of octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam-pulverizing process 2 Weight) to prepare the titanium dioxide pigment for the glass fiber reinforced modified plastic.
Comparative example 5
As in example 3, except in step 1.3: adding 4% KH550 (using gamma-aminopropyl triethoxy silane coupling agent to occupy TiO) in the steam powder process 2 Weight).
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the solution is dissolved by hydrochloric acid with the mass concentration of 20% or sodium hydroxide with the mass concentration of 20%Controlling pH value of the solution at 5, and curing for 90min.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of the filter cake is 18000 Ω & cm, drying and steam-pulverizing, and adding 4% KH550 (gamma-aminopropyl triethoxy silane coupling agent accounts for TiO) in the steam-pulverizing process 2 And (3) preparing the titanium dioxide pigment for the glass fiber reinforced modified plastic by weight.
Comparative example 6
As in example 3, except in step 1.3: adding 4% of G-132 monoalkoxy fatty acid titanate coupling agent (the coupling agent accounts for TiO) in the steam powder process 2 Weight).
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90 minutes.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of a filter cake is 18000 Ω & cm, then drying and steam-powder treatment, and adding 4% of G-132 monoalkoxy fatty acid titanate coupling agent (the coupling agent accounts for the weight of TiO 2) in the steam-powder process to prepare the titanium dioxide pigment for the glass fiber reinforced modified plastic.
Comparative example 7
As in example 3, except in step 1.2: adjusting the pH value of the slurry to 3 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight) S in the thiourea solution and Zn in the zinc nitrate solutionThe molar ratio is 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L in terms of Zn, the concentration of the thiourea solution is 40g/L in terms of S, and meanwhile, the pH value is controlled to be 3 by using 20% hydrochloric acid with mass concentration or 20% sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90min.
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 3 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 8% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 3 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the curing is carried out for 90 minutes.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of the filter cake is 18000 Ω & cm, drying and steam-pulverizing, and adding 4% of octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam-pulverizing process 2 Weight) to produce titanium dioxide pigment.
Comparative example 8
As in example 3, except in step 1.2: 1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 2% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution, wherein the molar ratio of the S in the thiourea solution to the Zn in the zinc nitrate solution is 1.8:1, the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90 minutes.
1.1A rutile type titanium dioxide primary product prepared by a chloridizing process is pulped by deionized water, the primary product is prepared into titanium dioxide slurry with the mass concentration of 23 percent, the temperature is raised to 75 ℃, and the temperature is maintained in the whole coating process.
1.2, adjusting the pH value of the slurry to 5 by using hydrochloric acid with the mass concentration of 20% or sodium hydroxide solution with the mass concentration of 20%; the thiourea solution and the 2% zinc nitrate solution (the addition amount of the zinc nitrate solution is that Zn occupies TiO) are added in 3.5 hours 2 Weight percent) of S in the thiourea solution and Zn in the zinc nitrate solution are 1.8:1, wherein the concentration of the zinc nitrate solution is 50g/L based on Zn, the concentration of the thiourea solution is 40g/L based on S, and meanwhile, the pH value is controlled to be 5 by using 20 percent hydrochloric acid with mass concentration or 20 percent sodium hydroxide solution with mass concentration, and the thiourea solution is cured for 90 minutes.
1.3 washing the cured slurry in the step (2) with deionized water at 75 ℃ until the conductivity of the filter cake is 18000 Ω & cm, drying and steam-pulverizing, and adding 4% of octyl triethoxy silane coupling agent (the silane coupling agent accounts for TiO) in the steam-pulverizing process 2 Weight) to produce titanium dioxide pigment.
As can be seen from the transmission electron micrographs of example 3 and comparative example 4, the surface coating film layer of the sample of example 3 is uniform and compact; in contrast, in comparative example 4, the film layer was unevenly and continuously formed, and the coating substance was nucleated independently.
The results of detecting the titanium dioxide pigments prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1. The indexes of impact resistance, whiteness and weather resistance are the test results that the product is added into a glass fiber reinforced modified nylon resin system according to the condition that titanium dioxide accounts for 2% of the total mass of the glass fiber reinforced modified nylon resin system, and is molded into a spline; the weather resistance index is the result of aging of the product sample bar in a xenon lamp for 600 hours.
Table 1 shows the relevant and application indexes of the products in examples and comparative examples.
From the comparison of table example 1-example 3 above, it can be seen that: the related key indexes and application indexes of the three samples have small difference; the higher the impact resistance index is, the smaller the impact of the titanium dioxide on the impact resistance is; the lower the weather resistance index, the better the zinc sulfide coating.
Comparative examples 1-8 parallel experiments were performed based on example 3. As can be seen from the comparison result of the comparative example 1 and the example 3, after the coating of zinc sulfide is canceled, the impact resistance and weather resistance of the product are obviously reduced; as can be seen from the comparison result of the comparative example 2 and the example 3, the organic surface treatment of the product is canceled, the impact resistance of the product is reduced, but the weather resistance is hardly affected; as can be seen from the comparison result of the comparative example 3 and the example 3, after the treatment of the organic treating agent for coating zinc sulfide and silane is canceled, the impact resistance and weather resistance of the product are obviously reduced; in comparative example 4, the water-soluble zinc salt solution and the water-soluble inorganic sulfide solution are adopted to react to prepare the zinc sulfide modified titanium dioxide pigment, and the inorganic water-soluble zinc salt solution and the water-soluble inorganic sulfide are adopted in the method, so that the reaction speed of zinc ions and sulfur ions is high due to the fact that the ionization speed of zinc ions and sulfur ions is high, and a uniform and compact zinc sulfide coating layer is difficult to form, and therefore, the titanium dioxide pigment prepared by the method has a certain gap between the material performance of products in glass fiber reinforced modified plastics and the material performance of titanium dioxide products which are not added. As can be seen from the comparison result of the comparative example 4 and the example 3, the change of organic sulfide to replace inorganic sulfide can lead the zinc sulfide coating coated on the surface of the titanium dioxide to be uniform and the compactness to be improved, which is completely consistent with the conclusion of fig. 1, and the uniform and compact zinc sulfide film layer can further improve the shock resistance of the glass fiber reinforced nylon; as can be seen from the comparison of comparative examples 5 and 6 with example 3, changing the type of the organic treatment agent coated on the product has a certain influence on the impact resistance of the composite material. As can be seen from the comparison result of the comparative example 7 and the example 3, too low coating pH value can cause low zinc sulfide coating rate and can cause certain adverse effect on the impact resistance of the composite material; as can be seen from the comparison result of the comparative example 8 and the example 3, the coated zinc sulfide content is too low, and the impact resistance of the composite material is adversely affected.
Therefore, the titanium dioxide pigment produced by the specific preparation method has high whiteness, excellent weather resistance and material performance, and can be widely used in the fields of high-quality plastics such as glass fiber reinforced modified plastics and the like; the titanium dioxide pigment prepared by the method has low production cost and high raw material utilization rate, and is beneficial to energy conservation and environmental protection.
The above is only a specific embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a special titanium dioxide pigment for glass fiber reinforced nylon is characterized by comprising the following steps: the method comprises the following specific steps:
(1) Beating the rutile type titanium dioxide primary product to obtain titanium dioxide slurry, heating to 70-80 ℃, and maintaining the temperature in the whole coating process;
(2) Regulating the pH value of the titanium dioxide slurry to 4-5.4 by using inorganic acid or inorganic alkali solution; adding a water-soluble zinc salt solution and a water-soluble organic sulfide solution within a certain time, wherein the addition amount of the water-soluble zinc salt solution is 5-10% by weight of Zn accounting for TiO2, and the molar ratio of S in the water-soluble organic sulfide solution to Zn in the water-soluble zinc salt solution is 1.5:1-2:1; simultaneously, inorganic acid or inorganic alkali solution is used for keeping the pH value at 4-5.4, and curing is carried out for 60-120 min;
(3) Washing the cured slurry obtained in the step (2) with deionized water at 70-80 ℃ until the conductivity of a filter cake is more than 15000 Ω & cm, drying and steam-powder treatment, and adding TiO in the steam-powder process 2 2-5% of silane coupling agent, wherein the silane coupling agent is at least one of octyl triethoxysilane and amyl triethoxysilane, and the special titanium dioxide pigment for glass fiber reinforced modified plastics is prepared.
2. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the water-soluble organic sulfide solution in the step (2) is thiourea solution.
3. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the water-soluble zinc salt solution is at least one of zinc nitrate solution, zinc sulfate solution, zinc chloride solution and zinc acetate solution.
4. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the concentration of the water-soluble zinc salt solution is 20-g/L to 100g/L calculated by Zn.
5. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the concentration of the water-soluble organic sulfide solution is 30 g/L-50 g/L in terms of S.
6. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the water-soluble zinc salt solution and the water-soluble organic sulfide solution are added for 3-4 hours.
7. The method for preparing the special titanium dioxide pigment for glass fiber reinforced nylon, which is characterized in that: the inorganic alkali solution in the step (2) is at least one of sodium hydroxide solution and potassium hydroxide solution, and the mass concentration of the inorganic alkali solution is 20%.
8. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the inorganic acid solution in the step (2) is at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution and phosphoric acid solution, and the mass concentration of the inorganic acid solution is 20%.
9. The method for preparing the glass fiber reinforced nylon special-purpose titanium dioxide pigment according to claim 1, which is characterized in that: the rutile type titanium dioxide primary product is a chloride process rutile type titanium dioxide primary product, and the concentration of the titanium dioxide slurry is 20% -25%.
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