阅读说明：本技术 一种用于水性自行车漆的树脂及其制备方法与应用 (Resin for water-based bicycle paint and preparation method and application thereof ) 是由 王海艳 杨伟明 叶维雪 于 2020-11-24 设计创作，主要内容包括：本发明提供了一种用于水性自行车漆的树脂的制备方法,包括以下步骤：S1、准备原料并将原料混合,原料包括对苯二甲酸、间苯二甲酸、己二酸、新戊二醇、有机铋以及二丁基羟基甲苯；S2、通入氮气,升温到130℃,保温一小时；S3、继续升温至210℃,维持5-8小时,保温酯化至体系透明；S4、降温至150℃,加入入偏苯三酸酐,升温到170-180℃并保温反应；S5、降温至120℃,加入有机硅氧烷,保温1小时；S6、添加环氧磷酸酯,然后保温2小时,S7、降温后得到合成树脂,最后将合成树脂与去离子水混合均匀,得到本发明所公布的水性自行车漆,具有良好的的耐水性、耐盐雾性,产品与底材的附着力优秀,配漆后VOC接近零,重涂性好,耐冲击性好。(The invention provides a preparation method of resin for water-based bicycle paint, which comprises the following steps: s1, preparing raw materials and mixing the raw materials, wherein the raw materials comprise terephthalic acid, isophthalic acid, adipic acid, neopentyl glycol, organic bismuth and dibutyl hydroxy toluene; s2, introducing nitrogen, heating to 130 ℃, and preserving heat for one hour; s3, continuously heating to 210 ℃, maintaining for 5-8 hours, and carrying out heat preservation esterification until the system is transparent; s4, cooling to 150 ℃, adding trimellitic anhydride, heating to 170-180 ℃, and carrying out heat preservation reaction; s5, cooling to 120 ℃, adding organic siloxane, and keeping the temperature for 1 hour; s6, adding epoxy phosphate, then preserving heat for 2 hours, S7, cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin and deionized water to obtain the water-based bicycle paint disclosed by the invention, wherein the water-based bicycle paint has good water resistance and salt spray resistance, the adhesion between the product and a substrate is excellent, the VOC after paint preparation is close to zero, the recoatability is good, and the impact resistance is good.)

1. A method for preparing a resin for an aqueous bicycle paint, comprising the steps of:

s1, preparing and mixing the raw materials;

s2, introducing nitrogen, heating to 140 ℃ at 120-;

s3, continuously heating to 200 ℃ and 220 ℃, maintaining for 5-8 hours, and carrying out heat preservation and esterification until the system is transparent;

s4, cooling to 140-;

s5, cooling to 115 ℃ and 125 ℃, adding organic siloxane, and keeping the temperature for 0.5-1.5 hours;

s6, adding epoxy phosphate, and then preserving heat for 1.5-2.5 hours;

s7, cooling to obtain the product,

the raw materials comprise terephthalic acid, isophthalic acid, adipic acid, neopentyl glycol, a catalyst and an antioxidant.

2. The method according to claim 1, wherein the reaction end point of the esterification reaction in S3 is a stable acid value of 6.0-7.0.

3. The method as claimed in claim 1, wherein the time for the heat-preserving reaction in S4 is 2 to 3 hours.

4. The method of claim 1, wherein the organosiloxane of S5 is epoxy silane (KH560), amino silane (KH550), or a mixture thereof.

5. The method of claim 4, wherein the epoxy silane and the aminosilane are mixed in a ratio of 1:10 to 10: 1.

6. The method of claim 1, wherein the catalyst is an organobismuth or organotin.

7. The process of claim 1, wherein the antioxidant is dibutylhydroxytoluene.

8. The method according to claim 1, wherein the epoxy phosphate is added in an amount of 8-10% by weight based on the total weight of the raw materials.

9. An aqueous bicycle paint using the resin obtained by the method of any one of claims 1 to 8, wherein the resin is obtained by mixing a synthetic resin with water in a mixing ratio of 1:1 to 1: 10.

10. The bicycle paint according to claim 9, wherein the water is deionized water having a conductivity of 18 μ S/cm or less.

Technical Field

The invention belongs to the technical field of organic polymer synthesis, and particularly relates to a resin for a water-based bicycle paint, and a preparation method and application thereof.

Background

The bicycle paint is a paint for coating bicycles, and currently, oil-based bicycle paint is generally adopted in the bicycle industry.

The use of the oily vehicle paint can cause the emission of a large amount of organic volatile compounds, thereby not only damaging the environment and harming the health of people, but also wasting resources and energy.

In consideration of energy conservation and environmental protection, the development of water-based vehicle paint for bicycles to replace oil-based vehicle paint is imperative, and the existing water-based product has the problems of low drying speed, insufficient flexibility (incapable of passing a ball drop experiment), incapable of recoating and the like, and cannot be used in large batch all the time.

Therefore, the development of the water-based bicycle paint which meets the requirement of environmental protection, can meet the requirement of a bicycle coating process and has excellent properties such as flexibility, corrosion resistance, recoatability and the like is particularly necessary for meeting the increasingly developed requirements of the bicycle industry.

Disclosure of Invention

The invention aims to overcome the defects of the existing bicycle paint and provide the water-based bicycle paint which can meet the requirements of a bicycle coating process and has excellent properties such as flexibility, corrosion resistance, recoatability and the like.

The technical scheme of the invention is as follows.

A method of preparing a resin for use in an aqueous bicycle paint, comprising the steps of:

s1, preparing and mixing the raw materials;

s2, introducing nitrogen, heating to 140 ℃ at 120-;

s3, continuously heating to 200 ℃ and 220 ℃, maintaining for 5-8 hours, and carrying out heat preservation and esterification until the system is transparent;

s4, cooling to 140-;

s5, cooling to 115 ℃ and 125 ℃, adding organic siloxane, and keeping the temperature for 0.5-1.5 hours;

s6, adding epoxy phosphate, and then preserving heat for 1.5-2.5 hours;

s7, cooling to obtain the product,

the raw materials comprise terephthalic acid, isophthalic acid, adipic acid, neopentyl glycol, a catalyst and an antioxidant.

Preferably, the reaction end point of the esterification reaction in S3 is a stable acid value of 6.0 to 7.0.

Preferably, the time for the heat-preservation reaction in S4 is 2 to 3 hours.

Preferably, the organosiloxane in S5 is epoxy silane (KH560), amino silane (KH550) or a mixture of the two.

Preferably, the mixing ratio of the epoxy silane to the amino silane is 1:10 to 10: 1.

Preferably, the catalyst is organic bismuth or organic tin.

Preferably, the antioxidant is dibutylhydroxytoluene.

Preferably, the addition amount of the epoxy phosphate is 8-10% of the total weight of the raw materials.

The invention also discloses a water-based bicycle paint which is prepared by mixing the synthetic resin and water in a mixing ratio of 1:1 to 1: 10.

Preferably, the water is deionized water, and the conductivity of the deionized water is less than or equal to 18 mu S/cm.

Compared with the prior art, the invention has the beneficial effects that: the flexible material adipic acid is selected, the formula and the production process of the raw materials are adjusted, the molecular components and the molecular structure of the synthetic resin are effectively controlled by adjusting the raw materials and adjusting the reaction time and the reaction conditions, more importantly, organic siloxane and phosphate groups are introduced, the crosslinking density of the synthetic resin is effectively increased, the product has flexibility and toughness, and meanwhile, the product has good water resistance and salt spray resistance, the adhesive force between the product and a substrate is excellent, Volatile Organic Compounds (VOC) after paint preparation is close to zero, the recoatability is good, the impact resistance is good, the product can completely replace similar oily products, and the industrial problem is solved.

Detailed Description

The following further illustrates embodiments of the invention:

a method of preparing a resin for use in an aqueous bicycle paint, comprising the steps of:

s1, adding raw materials into the reaction kettle, wherein the raw materials comprise terephthalic acid, isophthalic acid, adipic acid, neopentyl glycol, organic bismuth and dibutyl hydroxy toluene;

s2, introducing nitrogen, raising the temperature in the reaction kettle to 130 ℃, and preserving the temperature for one hour;

s3, continuously heating to 210 ℃, maintaining for 6.5 hours, preserving heat and esterifying until the acid value is stabilized at 6.5, and the system is transparent;

s4, cooling to 150 ℃, adding trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation;

s5, cooling to 120 ℃, adding organosiloxane which is a mixture of epoxy silane (KH560) and aminosilane (KH550), and keeping the temperature for 1 hour;

s6, adding epoxy phosphate in a dropwise manner, completing the addition of the epoxy phosphate within one hour, and then preserving the heat for 2 hours

And S7, cooling to obtain the product.

In order to make the objects and advantages of the invention more concise, the invention will be described in more detail with reference to the following examples, to which it is in no way limited. The following examples are merely preferred examples of the present invention and are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Example 1

Adding 200 kg of terephthalic acid, 200 kg of isophthalic acid, 100 kg of adipic acid, 550 kg of neopentyl glycol, 1 kg of organic bismuth and 2 kg of dibutyl hydroxy toluene into a reaction kettle, introducing nitrogen, heating to 130 ℃, preserving heat for 1 hour, heating to 210 ℃ for 8 hours, preserving heat, esterifying until the acid value is stabilized at 6.5, and the system is transparent; then cooling to 150 ℃, adding 30 kg of trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation; then cooling to 120 ℃, adding 10 kg of a 1:1 mixture of epoxy silane (KH560) and amino silane (KH550), preserving heat for 1 hour, then dripping 88 kg of epoxy phosphate, completing dripping for 1 hour, preserving heat for 2 hours, then cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin and deionized water to obtain the water-based bicycle paint disclosed by the invention.

Example 2

Adding 200 kg of terephthalic acid, 200 kg of isophthalic acid, 100 kg of adipic acid, 550 kg of neopentyl glycol, 1 kg of organic bismuth and 2 kg of dibutyl hydroxy toluene into a reaction kettle, introducing nitrogen, heating to 130 ℃, preserving heat for 1 hour, heating to 210 ℃ for 8 hours, preserving heat, esterifying until the acid value is stabilized at 6.5, and the system is transparent; then cooling to 150 ℃, adding 30 kg of trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation; then cooling to 120 ℃, adding 10 kg of a 1:1 mixture of epoxy silane (KH560) and amino silane (KH550), preserving heat for 1 hour, then dripping 108 kg of epoxy phosphate, completing dripping for 1 hour, preserving heat for 2 hours, then cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin and deionized water to obtain the water-based bicycle paint disclosed by the invention.

Example 3

Adding 200 kg of terephthalic acid, 200 kg of isophthalic acid, 100 kg of adipic acid, 550 kg of neopentyl glycol, 1 kg of organic bismuth and 2 kg of dibutyl hydroxy toluene into a reaction kettle, introducing nitrogen, heating to 130 ℃, preserving heat for 1 hour, heating to 210 ℃ for 8 hours, preserving heat, esterifying until the acid value is stabilized at 6.5, and the system is transparent; then cooling to 150 ℃, adding 30 kg of trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation; then cooling to 120 ℃, adding 10 kg of a 1:0.5 mixture of epoxy silane (KH560) and amino silane (KH550), preserving heat for 1 hour, dripping 108 kg of epoxy phosphate for 1 hour, preserving heat for 2 hours, cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin and deionized water to obtain the water-based bicycle paint disclosed by the invention.

Example 4

Adding 200 kg of terephthalic acid, 200 kg of isophthalic acid, 100 kg of adipic acid, 550 kg of neopentyl glycol, 1 kg of organic bismuth and 2 kg of dibutyl hydroxy toluene into a reaction kettle, introducing nitrogen, heating to 130 ℃, preserving heat for 1 hour, heating to 210 ℃ for 8 hours, preserving heat, esterifying until the acid value is stabilized at 6.5, and the system is transparent; then cooling to 150 ℃, adding 30 kg of trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation; then cooling to 120 ℃, adding 10 kg of epoxy silane (KH560), preserving heat for 1 hour, dripping 88 kg of epoxy phosphate, finishing dripping for 1 hour, preserving heat for 2 hours, then cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin with deionized water to obtain the water-based bicycle paint disclosed by the invention.

Example 5

Adding 200 kg of terephthalic acid, 200 kg of isophthalic acid, 100 kg of adipic acid, 550 kg of neopentyl glycol, 1 kg of organic bismuth and 2 kg of dibutyl hydroxy toluene into a reaction kettle, introducing nitrogen, heating to 130 ℃, preserving heat for 1 hour, heating to 210 ℃ for 8 hours, preserving heat, esterifying until the acid value is stabilized at 6.5, and the system is transparent; then cooling to 150 ℃, adding 30 kg of trimellitic anhydride, heating to 175 ℃, and reacting for 2.5 hours under the condition of heat preservation; then cooling to 120 ℃, adding 10 kg of epoxy silane (KH560), preserving heat for 1 hour, dripping 1 kg of epoxy phosphate, finishing dripping for 1 hour, preserving heat for 2 hours, then cooling to obtain synthetic resin, and finally uniformly mixing the synthetic resin with deionized water to obtain the water-based bicycle paint disclosed by the invention.

Examples of Performance testing

The water-based bicycle paints obtained in the above examples and commercially available oil-based bicycle paints were subjected to a repainting test, a salt spray resistance test, a 1.7 m ball drop test and an adhesion test (in accordance with GB9286, cross-hatch method), respectively, to obtain the following data tables:

comparative table of example Properties

The oil-based bicycle paint is purchased from paint manufacturers, Inc. in Jiangmen, and as can be seen from the above table, the oil-based bicycle paint of the present invention has no oil-based bicycle paint transmission in recoatability and salt spray resistance, and is better than the commercially available oil-based bicycle paint in adhesion, although the flexibility of the products of some examples is poor (the products cannot pass the ball drop test of 1.7 meters), the performances of examples 2 and 5 are better than those of similar oil-based products, and in view of cost, the preferred example 2 is the best example.

Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.