CN102295846A - Modified titanium white and preparation method thereof as well as automobile primer paint - Google Patents
Modified titanium white and preparation method thereof as well as automobile primer paint Download PDFInfo
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- CN102295846A CN102295846A CN2010102164578A CN201010216457A CN102295846A CN 102295846 A CN102295846 A CN 102295846A CN 2010102164578 A CN2010102164578 A CN 2010102164578A CN 201010216457 A CN201010216457 A CN 201010216457A CN 102295846 A CN102295846 A CN 102295846A
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Abstract
The invention provides modified titanium white which comprises titanium dioxide and polyacrylic acid coated on the surface of titanium dioxide, wherein the molecular weight of polyacrylic acid is 6000-8000. The invention also provides a preparation method of the modified titanium white and an automobile primer paint containing the modified titanium white. According to the invention, the titanium dioxide in the modified titanium white has powerful bond with polyacrylic acid, has good dispersibility in an organic system, and can be used in the field of automobile primer paints. In addition, in the invention, the modified titanium white is prepared by a dry method, the process is simple, and the cost is low.
Description
Technical field
The invention belongs to the titanium dioxide field, relate in particular to a kind of modified titanium and preparation method thereof, contain in the automobile of this modified titanium and be coated with coating.
Background technology
Titanium dioxide is a kind of mineral compound, through have good opacifying power, specific refractory power after the surface modification and in hydrophilic medium stronger dispersiveness, therefore in coating with lacquer, purposes is widely arranged at car surface.At present, the modified technique of titanium dioxide is divided into wet method and two kinds of dry method: wet method is about to titanium dioxide and disperses into suspension, then inorganic coating and organic coated is carried out on its surface; Dry method is promptly directly carried out coating to the titanium dioxide of powder shaped.In the prior art, when adopting the dry method coating, organic modifiers and TiO
2The particle bonding force is relatively poor, disengaging, and modified technique complexity easily, condition harshness; Organic modifiers commonly used is generally organic coated dose and comprises trihydroxy methyl propane, organic silicon surfactant, silane coupling agent.
For example, CN1680491A discloses a kind of method of dried preparation chemical fibre of titanium dioxide, with titanium dioxide is raw material, by superfine grinding, obtain superfine titanium white after the classification processing treatment, then by pressurized air with superfine titanium white and tensio-active agent be dispersed into respectively gas-solid logistics gentle-the mist logistics, importing is run affairs and is carried out the high-speed rotational motion in the swirler, finish the high efficient mixed collision, adhere to and classification, obtain the titanium dioxide adherend of different stage, at last by gas-solid separation, ageing is handled and is obtained the chemical fibre of titanium dioxide product of particle diameter＜1 μ m and the chemical fibre of titanium dioxide product of particle diameter 1-2 μ m.But the modified technique complexity of this chemical fibre of titanium dioxide, need earlier to titanium dioxide pulverize, the classification pre-treatment, and superfine titanium white and tensio-active agent all need to disperse by pressurized air, also need eddy flow collision classification at last, equipment cost is also higher.
Summary of the invention
The invention solves titanium dioxide modified technique complexity, cost technical problems of high in the prior art.
The invention provides a kind of modified titanium, described modified titanium comprises titanium dioxide and is coated on the polyacrylic acid of titanium dioxide surface; Described polyacrylic molecular weight is 6000-8000.
The invention provides a kind of preparation method of described modified titanium, comprise that elder generation under whipped state, sprays into vaporific surface-modifying agent in elementary titanium dioxide, change depolymerization in the airflow milling then over to, obtain described modified titanium; Described surface-modifying agent is polyacrylic acid and propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, and wherein polyacrylic molecular weight is 6000-8000.
The invention provides coating in a kind of automobile, contain matrix resin, pigment and thinner in the described automobile in the coating, contain or do not contain auxiliary agent, wherein, contain modified titanium provided by the invention in the described pigment.
It is that the polyacrylic acid of 6000-8000 and propyl carbinol are as surface-modifying agent that the present invention adopts molecular weight, directly elementary titanium dioxide is carried out the dry method coating under the whipped state, because the bonding force of polyacrylic acid and titanium dioxide surface is bigger, make polyacrylic acid evenly coat also in conjunction with tight at titanium dioxide surface, thereby realize the organic coated of titanium dioxide surface, depolymerization obtains modified titanium of the present invention then.The bonding force of modified titanium surface organic film of the present invention and titanium dioxide granule is very high, makes modified titanium dispersed fine in organic system, can be used for being coated with in the automobile paint field.The preparation technology of modified titanium provided by the invention is very simple, and cost is reduced greatly.
Embodiment
The invention provides a kind of modified titanium, described modified titanium comprises titanium dioxide and is coated on the polyacrylic acid of titanium dioxide surface; Described polyacrylic molecular weight is 6000-8000.
Modified titanium provided by the invention, polyacrylic acid is coated on titanium dioxide surface, and polyacrylic molecular weight is 6000-8000.Polyacrylic structural formula is [CH
2-CH (COOH)]
n, a large amount of carboxyls are arranged on the side chain, the titanium dioxide surface possess hydrophilic property is the poly-hydroxy state, and polyacrylic acid and titanium dioxide are by the chemical bond-linking of carboxyl and hydroxyl, thus the realization polyacrylic acid obtains modified titanium of the present invention in the coating of titanium dioxide surface.The present inventor finds that by a large amount of experiments polyacrylic molecular weight is excessive, can cause the viscosity of surface-modifying agent system excessive, meeting plug nozzle during spraying; And molecular weight is too small, and it is less to contain the carboxyl number, and is less with the bonding force of titanium dioxide, the modified titanium instability that obtains.In addition, among the present invention, polyacrylic acid can not adopt polyacrylic salt, can cause the titanium dioxide efflorescence.
In the modified titanium provided by the invention, titanium dioxide and polyacrylic mass ratio are 1: 0.008-0.012, more preferably 1: 0.01.
The preparation method of modified titanium of the present invention comprises that elder generation under whipped state, sprays into vaporific surface-modifying agent in elementary titanium dioxide, changes depolymerization in the airflow milling then over to, obtains described modified titanium; Described surface-modifying agent is polyacrylic acid and low boiling point organic solvent, and wherein polyacrylic molecular weight is 6000-8000.
Preparation method's of the present invention mechanism is: elementary titanium dioxide is under whipped state, polyacrylic molecule contacts with titanium dioxide by Sprayable, and, by air-flow titanium dioxide is carried out depolymerization then attached to titanium dioxide surface, obtain the modified titanium of uniform particle diameter.
Wherein, surface-modifying agent of the present invention is the mixed system of polyacrylic acid and low boiling point organic solvent, and low boiling point organic solvent is used to disperse polyacrylic acid, volatilizees during depolymerization in airflow milling, and titanium dioxide surface only is attached with polyacrylic acid.In the described surface-modifying agent, be uniformly dispersed for making polyacrylic acid, the mass ratio of polyacrylic acid and low boiling point organic solvent is 1: 1.1-1.4.Wherein, described low boiling point organic solvent for example can be selected from propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol for well known to a person skilled in the art that boiling point is lower than 100 ℃ of organic solvents under a normal atmosphere.
Elementary titanium dioxide with 100 weight parts is a benchmark, and the consumption of surface-modifying agent is the 2.1-2.4 weight part.
The spray process of described surface-modifying agent can adopt right angle circular cone nozzle to carry out.For example, elementary titanium dioxide is placed high-speed mixer and mixing, then one of right angle circular cone nozzle is terminated on the high mixer, surface-modifying agent is sprayed in the elementary titanium dioxide of stirring by the fog system that links to each other with the right angle circular cone nozzle the other end.Wherein, nozzle pressure is lower than 0.9Mpa, and mist flow is 1.0-1.4L/min.
After spraying is finished, mixed system is changed in the airflow milling, obtain modified titanium of the present invention by the airflow milling depolymerization.Wherein, the temperature of depolymerization is 100-140 ℃, and air pressure is 1.0-1.4Mpa.Described airflow milling can adopt airflow milling common in the prior art, for example the collision type airflow milling of Shenyang aircraft factory production.
Modified titanium preparation technology of the present invention is simple, and therefore the various excellent performances of the modified titanium that obtains have wider Application Areas.For example, modified titanium of the present invention can be used as pigment and is used for paint field.
The invention provides coating in a kind of automobile, contain matrix resin, pigment and thinner in the described automobile in the coating, contain or do not contain auxiliary agent, wherein, contain modified titanium provided by the invention in the described pigment.
As those skilled in the art's common practise, the coating that coating forms in the automobile is used to fill the not plane of car panel and priming paint between vehicle paint base and finish paint, reduces finish paint thickness, increases the finish paint fullness ratio.In the characteristics of coating be that pigment is more, so the quality of the quality centering coating layer of pigment has very big influence.Contain modified titanium provided by the invention in the pigment that coating adopts in the automobile of the present invention, it has good dispersiveness, makes to adopt the various performances of the coating that coating forms in the automobile of the present invention all to meet the demands.
As those skilled in the art's common practise, described matrix resin is selected from one or more in melamine resin, butylated melamine resin, modified alkyd resin, the Resins, epoxy; Described thinner is selected from one or more in N-BUTYL ACETATE, dimethylbenzene, butanols, butanone, the butyl carbitol acetate.Can also contain various other pigment that those skilled in the art use always in the described pigment, for example carbon black, alkali formula plumbic acid are white, zinc chromate, barium sulfate or colloidal zinc oxide.
Quality with coating in the automobile is a benchmark, and the content of matrix resin is 40-80%, and the content of pigment is 10-30%, and the content of thinner is 10-30%.
The various auxiliary agents that described auxiliary agent is used always for those skilled in the art, for example flow agent.Described flow agent can directly adopt and be purchased product, for example can be BYK333,301, AFCONA3770,3605, the FC430 of 3M company; The preferred FC430 that adopts.Under the preferable case, be benchmark with the quality of coating in the automobile, the content of flow agent is 0.01-2%.
The preparation method of middle coating intermediate of the present invention for conventionally known to one of skill in the art, for example can mix various components obtaining; Also can be earlier with pigment and part matrix resin, mixing diluents preparation mill base, mill base and remaining ingredient are mixed obtain then.The present invention preferably adopts preparation mill base earlier, again with other component blended preparation method.
The present invention is further illustrated below in conjunction with embodiment.In embodiment and the Comparative Examples, the raw material that is adopted all is available commercially.
Embodiment 1
(1) 250g polyacrylic acid (molecular weight is 7000) and 300g propyl carbinol are mixed the preparation surface-modifying agent.
(2) the elementary titanium dioxide of 25kg is put in the high mixer, opened and stir; The surface-modifying agent of step (1) is passed through right angle circular cone nozzles spray on elementary titanium dioxide, and nozzle pressure is 0.7Mpa, and mist flow is 1.2L/min;
(3) after continuing to stir 10min after sprinkling is finished, change in the collision type airflow milling, air pressure 1.2MPa, 120 ℃ of following depolymerization 30min collect the modified titanium that discharging obtains present embodiment, are designated as T1.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare the modified titanium of present embodiment, difference is:
In the step (1), polyacrylic acid 250g (molecular weight is 8000), propyl carbinol 350g, quality is than polyacrylic acid: propyl carbinol=1: 1.4.
By above-mentioned steps, obtain modified titanium, be designated as T2.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare the modified titanium of present embodiment, difference is:
In the step (2), the quality of elementary titanium dioxide is 31.25Kg, and quality is than titanium dioxide: polyacrylic acid=1: 0.008.
By above-mentioned steps, obtain modified titanium, be designated as T3.
Comparative Examples 1
Adopt CN1680491A embodiment 9 disclosed methods to prepare the chemical fibre of titanium dioxide DT1 of this Comparative Examples, the tensio-active agent of employing is: polymethyl acrylate 0.2kg+ sodium polyacrylate 0.2kg.
Embodiment 4
(1) according to the mill base J1 of the ratio of table 1 preparation present embodiment, wherein titanium dioxide adopts the modified titanium T1 of embodiment 1:
Table 1
(2) mixed that mill base J1 and all the other each components of step (1) preparation press table 2 is even, and mistake 400 eye mesh screens obtain coating S1 in the automobile of present embodiment:
Table 2
Embodiment 5-6
Adopt the step identical with embodiment 4 to prepare coating in the automobile of embodiment 5-6 respectively, difference is that titanium dioxide adopts modified titanium T2, the T3 of embodiment 2,3 respectively, and coating is designated as S2, S3 successively in the automobile that obtains.
Comparative Examples 2
Adopt the step identical with embodiment 4 to prepare coating in the automobile of this Comparative Examples respectively, difference is, the chemical fibre of titanium dioxide powder DT1 of titanium dioxide employing Comparative Examples 1, and coating is designated as DS1 successively in the automobile that obtains.
Comparative Examples 3
Adopt the step identical with embodiment 4 to prepare coating in the automobile of this Comparative Examples respectively, difference is, titanium dioxide adopts the CR826 type titanium dioxide of Australian Ke Meiji company, and coating is designated as DS2 successively in the automobile that obtains.
Performance test:
(1) with the coating test of sequence number 1-6 during coating S1-S3 and DS1-DS2 carry out tables 3 in the automobile, test result is as shown in table 3;
(2) coating S1-S3 and DS1-DS2 in the automobile are coated on the prime coat, solidify to form coating layer in the automobile, then coating layer in the automobile carry out table 3 respectively in the paint film test of sequence number 7-11, test result is as shown in table 3.
Table 3
| Sequence number | Test item | Standard | S1 | S2 | S3 | DS1 | DS2 |
| 1 | The container internal state | No foreign matter, skinning not stirs the no lump in back and is uniformly dispersed, and is designated as OK; Otherwise, be designated as NO. | OK | OK | OK | OK | OK |
| 2 | Delivery viscosity | 30-90S | 81 | 83 | 79 | 84 | 78 |
| 3 | The dilution viscosity | 30s | 30 | 30 | 30 | 30 | 30 |
| 4 | Gloss | / | / | / | / | / | / |
| 5 | Proportion (g/ml) | 1.2 ± 0.1 | 1.23 | 1.22 | 1.24 | 1.21 | 1.24 |
| 6 | Former lacquer fineness (μ m) | ≤ 17 | ≤ 17 | ≤ 17 | ≤ 17 | ≤ 17 | ≤ 17 |
| 7 | Paint film appearance | Smooth smooth, free of pinholes particle is designated as OK; Otherwise, be designated as NO. | OK | OK | OK | OK | OK |
| 8 | Sticking power | The 0-1 level | 0 | 0 | 0 | 0 | 0 |
| 9 | Hardness | 〉=HB | HB | HB | HB | HB | HB |
| 10 | Shock strength (kg * cm) | 〉=30 | 40 | 40 | 40 | 40 | 40 |
| 11 | Snappiness (mm) | 1 | 1 | 1 | 1 | 1 | 1 |
From the test result of last table 3 as can be seen, the modified titanium that adopts preparation method of the present invention to obtain use with automobile in be coated with paint field, the various performances of coating and the coating that obtained by this coating are all more excellent, reach effect same with titanium dioxide of the prior art, but the preparation technology of titanium dioxide of the present invention is simple, and is with low cost.
Claims (12)
1. modified titanium, described modified titanium comprise titanium dioxide and are coated on the polyacrylic acid of titanium dioxide surface; Described polyacrylic molecular weight is 6000-8000.
2. modified titanium according to claim 1 is characterized in that, described titanium dioxide and polyacrylic mass ratio are 1: 0.008-0.012.
3. the preparation method of the described modified titanium of claim 1 comprises that elder generation under whipped state, sprays into vaporific surface-modifying agent in elementary titanium dioxide, changes depolymerization in the airflow milling then over to, obtains described modified titanium; Described surface-modifying agent is polyacrylic acid and low boiling point organic solvent, and wherein polyacrylic molecular weight is 6000-8000.
4. method according to claim 3 is characterized in that, in the described surface-modifying agent, the mass ratio of polyacrylic acid and low boiling point organic solvent is 1: 1.1-1.4.
5. according to claim 3 or 4 described methods, it is characterized in that described low boiling point organic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.
6. according to claim 3 or 4 described methods, it is characterized in that, is benchmark with the elementary titanium dioxide of 100 weight parts, and the consumption of surface-modifying agent is the 1.68-2.88 weight part.
7. method according to claim 3 is characterized in that, the spray process of surface-modifying agent adopts right angle circular cone nozzle, and nozzle pressure is lower than 0.9Mpa, and mist flow is 1.0-1.4L/min.
8. method according to claim 3 is characterized in that: the temperature of depolymerization is 100-140 ℃, and air pressure is 1.0-1.4Mpa.
9. coating in the automobile contains matrix resin, pigment and thinner in the coating in the described automobile, contains or does not contain auxiliary agent, it is characterized in that, contains the described modified titanium of claim 1 in the described pigment.
10. coating in the automobile according to claim 9 is characterized in that described matrix resin is selected from one or more in melamine resin, butylated melamine resin, modified alkyd resin, the Resins, epoxy; Described thinner is selected from one or more in N-BUTYL ACETATE, dimethylbenzene, butanols, butanone, the butyl carbitol acetate.
11. coating in the automobile according to claim 9 is characterized in that, contains also in the described pigment that carbon black, alkali formula plumbic acid are white, in the zinc chromate, barium sulfate, colloidal zinc oxide one or more.
12. coating in the automobile according to claim 9 is characterized in that, is benchmark with the quality of coating in the automobile, the content of matrix resin is 40-80%, and the content of pigment is 10-30%, and the content of thinner is 10-30%.
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|---|---|---|---|
| CN201010216457.8A CN102295846B (en) | 2010-06-28 | 2010-06-28 | Modified titanium white and preparation method thereof as well as automobile primer paint |
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| CN201010216457.8A CN102295846B (en) | 2010-06-28 | 2010-06-28 | Modified titanium white and preparation method thereof as well as automobile primer paint |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151869A (en) * | 2014-07-10 | 2014-11-19 | 池州市英派科技有限公司 | Modified nano-titanium dioxide with tenacity and good damp-proof effect, and preparation method of modified nano-titanium dioxide |
| CN105348566A (en) * | 2015-11-26 | 2016-02-24 | 河北麦森钛白粉有限公司 | Preparation technology of nanometer titania and organic polymer coated coating |
| CN105623312A (en) * | 2016-01-05 | 2016-06-01 | 天津先光化工有限公司 | Method for preparing silicon-treated titanium dioxide through dry method |
| CN105860592A (en) * | 2016-05-05 | 2016-08-17 | 中钛集团洛阳市裕星化工有限公司 | Modified titanium dioxide powder with coated polyacrylic acid |
| CN107523097A (en) * | 2017-09-05 | 2017-12-29 | 攀钢集团重庆钛业有限公司 | A kind of pigment, titanium white compound powder, titanium dioxide and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151869A (en) * | 2014-07-10 | 2014-11-19 | 池州市英派科技有限公司 | Modified nano-titanium dioxide with tenacity and good damp-proof effect, and preparation method of modified nano-titanium dioxide |
| CN104151869B (en) * | 2014-07-10 | 2016-01-20 | 池州市英派科技有限公司 | A kind of have modified nano-titanium dioxide of good toughness moisture effect and preparation method thereof |
| CN105348566A (en) * | 2015-11-26 | 2016-02-24 | 河北麦森钛白粉有限公司 | Preparation technology of nanometer titania and organic polymer coated coating |
| CN105348566B (en) * | 2015-11-26 | 2018-05-08 | 河北麦森钛白粉有限公司 | A kind of preparation process of nano-titanium dioxide, organic polymer coating coating |
| CN105623312A (en) * | 2016-01-05 | 2016-06-01 | 天津先光化工有限公司 | Method for preparing silicon-treated titanium dioxide through dry method |
| CN105860592A (en) * | 2016-05-05 | 2016-08-17 | 中钛集团洛阳市裕星化工有限公司 | Modified titanium dioxide powder with coated polyacrylic acid |
| CN105860592B (en) * | 2016-05-05 | 2018-02-16 | 焦作市裕盛钛业有限公司 | A kind of modified titanium for being coated with polyacrylic acid |
| CN107523097A (en) * | 2017-09-05 | 2017-12-29 | 攀钢集团重庆钛业有限公司 | A kind of pigment, titanium white compound powder, titanium dioxide and preparation method thereof |
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| CN102295846B (en) | 2014-01-29 |
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