阅读说明：本技术 一种净味树脂、制备方法及应用 (Odor-free resin, preparation method and application ) 是由 方学平 杨长春 于 2020-12-30 设计创作，主要内容包括：本发明提供了一种净味树脂、制备方法及应用。一种净味树脂,制备原料包括氢化蓖麻油、月桂酸、苯酐、新戊二醇、三羟甲基丙烷、季戊四醇、二甲苯和丁酯。本发明提供的净味树脂,由于原料中添加了氢化蓖麻油,因此反应程度更高,所得净味树脂的耐候性和净味效果也更好；由于原料中包括了新戊二醇、三羟甲基丙烷等高透明多元醇,因此提升了所得净味树脂的透明度。(The invention provides odor-free resin, a preparation method and application. An odor-free resin is prepared from hydrogenated castor oil, lauric acid, phthalic anhydride, neopentyl glycol, trimethylolpropane, pentaerythritol, xylene and butyl ester. According to the odorless resin provided by the invention, as the hydrogenated castor oil is added into the raw materials, the reaction degree is higher, and the weather resistance and the odorless effect of the odorless resin are better; because the raw materials comprise high-transparency polyhydric alcohols such as neopentyl glycol and trimethylolpropane, the transparency of the obtained odorless resin is improved.)

1. The odor-free resin is characterized in that the preparation raw materials comprise hydrogenated castor oil, lauric acid, phthalic anhydride, neopentyl glycol, trimethylolpropane, pentaerythritol, xylene and butyl ester.

2. The odor purification resin as claimed in claim 1, wherein the preparation raw materials comprise, in mass percent:

3. the odorless resin of claim 1 which has a fineness of 12 μm or less.

4. The odor purification resin of claim 1, wherein the odor purification resin has a hydroxyl value of 115mg KOH/g to 125mg KOH/g.

5. The odor-reducing resin according to claim 1, wherein the viscosity of the odor-reducing resin is 15000mpa.s to 25000mpa.s at 25 ℃.

6. The odor purification resin of claim 1, wherein the mass percentage of solid matter in the odor purification resin is 78% to 82%.

7. A process for the preparation of an odour-reducing resin as claimed in any of claims 1 to 6, comprising the steps of:

s1, adding partial dimethylbenzene into a reaction container in a protective gas environment, adding lauric acid, hydrogenated castor oil, phthalic anhydride, neopentyl glycol, trimethylolpropane and pentaerythritol, heating to dissolve, stirring, and continuously heating to obtain a system A;

s2, stopping heating, closing protective gas, dropwise adding the residual dimethylbenzene into the system A, and continuing to react to obtain a system B;

s3, continuously heating and reacting the system B in a protective gas environment, and obtaining a system C when the viscosity is qualified;

and S4, mixing the cooled system C with the butyl ester to obtain the odorless resin.

8. The method according to claim 7, wherein the portion of xylene in step S1 is 25-75% of the total mass of xylene.

9. Use of the odour-reducing resin as claimed in any one of claims 1 to 6 in a coating.

10. The use according to claim 9, wherein the coating is a wood coating.

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to odorless resin, a preparation method and application.

Background

The paint is a special coating, and is a chemical mixture coating which can firmly cover the surface of an object and has the functions of protection, decoration, marking and other special purposes.

With the improvement of living standard, people have higher requirements on the environmental protection of the household coating. Therefore, compared with other types of coatings, the environmental-friendly odor-purifying type household coating is more popular with consumers.

The environment-friendly odor-purifying type resin is an important component of the environment-friendly odor-purifying type coating, but the coating prepared by the conventional environment-friendly odor-purifying type resin has the problems of poor gloss distribution uniformity, poor transparency and the like after being applied to the surface of furniture, so that a paint film is whitened, the grain property of wood cannot be exposed, and the ornamental property is poor. Due to the above problems, the conventional environmental-friendly odor-purifying type resin cannot meet the requirement of high transparency of high-grade furniture.

Disclosure of Invention

The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides the odorless resin, and the polymerization degree of the odorless resin is improved through the blending of the components, so that the odorless effect and the transparency of the polymer resin are improved.

In a second aspect, the invention provides a method for preparing an odorless resin.

In a third aspect of the invention, there is provided the use of an odour-reducing resin.

An odor-free resin is prepared from hydrogenated castor oil, lauric acid, phthalic anhydride, neopentyl glycol, trimethylolpropane, pentaerythritol, xylene and butyl ester.

According to some embodiments of the invention, the odorless resin is prepared from the following raw materials in percentage by mass:

according to some embodiments of the invention, the neat resin has a fineness of 12 μm or less.

According to some embodiments of the invention, the neat resin has a hydroxyl number of 115mg KOH/g to 125mg KOH/g.

The hydroxyl value is as follows: hydroxyl groups in 1g resin sample, corresponding to milligrams of potassium hydroxide (KOH).

The hydroxyl value is determined by the national standard document with the reference number of GB/T719321987: determination of hydroxyl value of unsaturated polyester resin.

According to some embodiments of the invention, the neat resin has a viscosity of from 15000mpa.s to 25000mpa.s (25 ℃).

The viscosity, test method reference number is GB/T7193.1-1987 national standard document: method for measuring viscosity of unsaturated polyester resin.

According to some embodiments of the invention, the mass percentage of solid matter in the odorless resin is 78% to 82%.

According to some embodiments of the invention, the neat resin appearance ≦ 1# (iron cobalt).

The appearance was measured with an iron-cobalt colorimeter. The iron-cobalt colorimeter consists of 18 standard color gradation solution tubes, wherein the lightest is 1#, and the deepest is 18 #.

According to some embodiments of the invention, the neat resin has an acid number of 15mgKOH/g or less.

The acid number refers to the mass of KOH consumed per gram of neat resin by the acid content.

The acid value and the test method refer to the national standard document with GB/T2895-1982: measurement of acid value of unsaturated polyester resin.

According to the odor-free resin provided by the invention, as the hydrogenated castor oil is added into the raw materials, in the high-temperature reaction process, the hydrogenated castor oil, the lauric acid, the neopentyl glycol and the trimethylolpropane have thermal polymerization reaction in addition to esterification reaction, so that the reaction degree of the raw materials is higher.

The odorless resin provided by the invention has higher reaction degree of raw materials, so that the coating containing the odorless resin has better uniformity and film forming effect; therefore, the weather resistance (the difficulty of damaging the coating by the weather environment), the odor-removing effect and the transparency are better.

A preparation method of the odorless resin comprises the following steps:

s1, adding partial dimethylbenzene into a reaction container in a protective gas environment, adding lauric acid, hydrogenated castor oil, phthalic anhydride, neopentyl glycol, trimethylolpropane and pentaerythritol, heating to dissolve, stirring, and continuously heating to obtain a system A;

s2, stopping heating, closing protective gas, dropwise adding the residual dimethylbenzene into the system A, and continuing to react to obtain a system B;

s3, continuously heating and reacting the system B in a protective gas environment, and obtaining a system C when the viscosity is qualified;

and S4, mixing the cooled system C with the butyl ester to obtain the odorless resin.

According to some embodiments of the present invention, the preparation method further includes checking whether the used equipment, the oil temperature system is normal, whether the reaction vessel is clean, and whether the bottom valve is closed before the step S1.

According to some embodiments of the invention, the protective gas environment is at least one of an inert gas or nitrogen.

According to some embodiments of the invention, in step S1, the reaction vessel is a reflux reactor.

According to some embodiments of the present invention, the preparation method further comprises performing gas replacement of the reaction vessel with 5L/min of a shielding gas for 20min before step S1.

According to some embodiments of the present invention, in step S1, the part of xylene is metered by the metering tank and then added into the reflux reactor; the lauric acid, the hydrogenated castor oil, the phthalic anhydride, the neopentyl glycol, the trimethylolpropane and the pentaerythritol are added through a solid feeding port of the reflux reaction kettle.

According to some embodiments of the invention, in step S1, the portion of xylene is 25% to 75% of the total mass of xylene.

According to some embodiments of the present invention, step S1 further comprises performing gas replacement on the system for 15min with 5L/min of protective gas before the start of the heating dissolution.

According to some embodiments of the invention, in step S1, the heating dissolves at a temperature of 120 ℃.

According to some embodiments of the invention, in step S1, before the start of stirring, the flow rate of the shielding gas is 5L/min; after the start of stirring, the flow rate was 1L/min.

According to some embodiments of the invention, in step S1, the temperature increase is continued, and the steps are divided into stage 1 and stage 2; the stage 1 refers to that the temperature is raised to 170 ℃ and the temperature raising time is 1-2 h; the stage 2 is to heat the temperature to 193-197 ℃ and keep the temperature for 2h, and the heating time is 1-2 h.

According to some embodiments of the invention, between stage 1 and stage 2, there is further included opening the vertical, horizontal condenser of the reflux reactor and adjusting the reflux water flow to 1/4 of the maximum flow.

The reason for adjusting the flow rate of the return water is that: after the stage 1 is completed, the reflux phenomenon occurs in the reflux reaction kettle, and the reflux water flow is adjusted in order to improve the reflux effect.

According to some embodiments of the present invention, in step S2, the remaining xylene is added into the water separator through the metering tank, and finally dropped into the reflux reaction kettle for 10min to 20 min.

Because the boiling point of the xylene is about 130 ℃, the system temperature is 193-197 ℃ before the residual xylene is dripped, the stirring speed needs to be reduced or the stirring needs to be stopped in order to avoid the expansion of the kettle caused by the rapid vaporization of the xylene, and the residual xylene needs to be dripped slowly.

According to some embodiments of the invention, in step S2, the reaction is continued for 5 min.

According to some embodiments of the present invention, in step S3, the heating reaction is performed by first raising the temperature to 193 ℃ to 197 ℃, maintaining the temperature for 1 hour, and then continuing raising the temperature to 208 ℃ to 212 ℃ at a rate of 10 ℃/hour, and then maintaining the temperature.

According to some embodiments of the invention, in step S3, the viscosity is sampled by: in the heating reaction process, when the viscosity is less than 20s, the sampling inspection is carried out once per hour, and when the viscosity is more than or equal to 20s, the sampling inspection is carried out once per half hour.

Because the rotary viscometer is used for testing the viscosity, the sample consumption is high and the required time is long; therefore, in step S3, the process viscosity is controlled by using the grignard viscosity test instead of the rotational viscometer test, so as to achieve the purpose of using less sample and rapidly grasping the state of the sample.

According to some embodiments of the invention, the viscosity is acceptable in step S3 and ranges from 30S to 40S.

According to some embodiments of the invention, the viscosity is acceptable in step S3 and ranges from 33S to 37S.

According to some embodiments of the invention, in step S4, the cooling is performed by turning on the cooling oil.

According to some embodiments of the invention, the temperature decrease in step S4 is a temperature decrease to about 165 ℃.

According to some embodiments of the invention, the preparation method further comprises filtering, weighing and packaging the odorless resin after the step S4.

According to some embodiments of the present invention, the reflux is performed during the reaction in steps S2 to S3.

An application of odorless resin in paint.

According to some embodiments of the invention, the coating is a wood coating.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) according to the odorless resin provided by the invention, as the hydrogenated castor oil is added into the raw materials, in the high-temperature reaction process, the hydrogenated castor oil, the lauric acid, the neopentyl glycol and the trimethylolpropane have thermal polymerization reaction in addition to esterification reaction, so that the reaction degree of the raw materials is higher, and the obtained odorless resin has better weather resistance, odor purification effect and transparency.

(2) According to the odorless resin provided by the invention, as the raw materials comprise high-transparency polyhydric alcohols such as neopentyl glycol and trimethylolpropane, and the like, and after esterification and polymerization are carried out under a high-temperature condition, the generated molecular structure has extremely high crystal transparency, so that the transparency of the obtained odorless resin is improved.

Detailed Description

The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.

Unless otherwise specified, reagents used in the embodiments are commercially available and have not been subjected to any pretreatment before use.

Example 1

In this example, a flavor-free resin is prepared, and the specific raw material formulation is shown in table 1, and the steps are as follows:

s1, checking a reflux reaction kettle, ensuring that a bottom valve is closed, the temperature is normal, and after the kettle is clean, introducing nitrogen at the flow rate of 5L/min for 20min to perform gas replacement in the reflux reaction kettle;

s2, adding dimethylbenzene a into a reflux reaction kettle through a metering kettle, performing gas displacement on the system for 15min by using nitrogen at 5L/min, adding lauric acid, hydrogenated castor oil, phthalic anhydride, neopentyl glycol, trimethylolpropane and pentaerythritol into the reflux reaction kettle through a solid feeding port, and sealing a feeding port; introducing nitrogen for 15min at the flow rate of 5L/min, and performing gas replacement in the reflux reaction kettle;

s3, heating the system obtained in the step S3 to 120 ℃ under the protection of nitrogen with the flow rate of 5L/min, and then refluxing the system; adjusting the flow speed of nitrogen to 1L/min, and starting stirring;

s4, keeping the speed of 1L/min, introducing nitrogen, and continuously stirring; simultaneously, heating the system obtained in the step S3 to 170 ℃ at a heating rate of 0.5 ℃/min; then opening a vertical condenser and a horizontal condenser of the reflux reaction kettle, and adjusting the flow of reflux water to 1/4 of the maximum flow; continuously heating to 195 ℃ at the heating rate of 0.25 ℃/min, and preserving the heat for 2h to obtain a system A;

s5, stopping heating, closing nitrogen, dropwise adding the dimethylbenzene B into the system A, and continuously reacting and refluxing for 5min to obtain a system B;

s6, heating the system B to 195 ℃ in a nitrogen atmosphere, preserving heat for 1h, then heating to 210 ℃ at a speed of 10 ℃/h, preserving heat for reaction, performing viscosity sampling inspection in the reaction process, performing sampling inspection once per hour when the viscosity is less than 20s, performing sampling inspection once per half hour when the viscosity is more than or equal to 20s, and stopping sampling inspection when the viscosity is 35s to obtain a system C;

and S7, opening the cooling oil in the reflux reaction kettle, cooling the system C to 165 ℃, transferring the system C to a diluting kettle, mixing the system C with butyl ester, filtering, packaging and weighing to obtain the odorless resin.

Table 1 shows the composition ratio of the odorless resin in terms of mass percent.

Example 2

The difference between the preparation of the odorless resin and the preparation of the odorless resin in the example 1 is that the raw material ratio is different, and the specific raw material ratio is shown in table 1.

Example 3

The difference between the preparation of the odorless resin and the preparation of the odorless resin in the example 1 is that the raw material ratio is different, and the specific raw material ratio is shown in table 1.

Example 4

The difference between the preparation of the odorless resin and the preparation of the odorless resin in the example 1 is that the raw material ratio is different, and the specific raw material ratio is shown in table 1.

Example 5

The difference between the preparation of the odorless resin and the preparation of the odorless resin in the example 1 is that the raw material ratio is different, and the specific raw material ratio is shown in table 1.

Example 6

The difference between the preparation of the odorless resin and the preparation of the odorless resin in the example 1 is that the raw material ratio is different, and the specific raw material ratio is shown in table 1.

Example of detection

The performance of the odor-free resin obtained in examples 1 to 6 was tested, and the specific test method and results are as follows.

The detection method comprises the following steps:

fineness, the reference number of the test method is GB/T1724-: coating fineness determination.

Hydroxyl value, test method reference number GB/T719321987 national standard documents: determination of hydroxyl value of unsaturated polyester resin.

Viscosity, test methods reference the national standard document GB/T7193.1-1987: method for measuring viscosity of unsaturated polyester resin.

Appearance, measured with an iron-cobalt colorimeter. The iron-cobalt colorimeter consists of 18 standard color gradation solution tubes, wherein the lightest is 1#, and the deepest is 18 #.

Acid value, test method reference number is GB/T2895-1982 national standard document: measurement of acid value of unsaturated polyester resin.

The test results are shown in table 2.

Table 2 results of the testing of neat resins.

Performance of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Fineness of mum	10	12	11	10	10	11
Hydroxyl value of mgKOH/g	122	121	120	125	124	120
							Viscosity mpa.s/25 deg.C	20200	20000	20250	20300	20180	20200
Mass fraction of solid matter	81.7％	81.9％	82％	81.85％	81.75％	81.9％
							Appearance of the product	≤1#	≤1#	≤1#	≤1#	≤1#	≤1#
Acid value mgKOH/g	6.0	6.1	6.3	6.0	5.9	5.9

From the results in Table 1, it is understood that the total content of xylene a, xylene b and butyl ester as solvents in the raw material is 17%, that is, the mass fraction of solid matter in the raw material is 83%, which is larger than the mass fraction of solid matter in the finished odorless resin shown in Table 2. The reasons for the above differences are: esterification reaction can occur during the heating process of the raw materials, and a certain amount of water can be generated through the esterification reaction, so the mass fraction of solid matters in the finished odorless resin can be reduced.

As is clear from the results shown in table 2, the odorless resin obtained by referring to the raw material formulation and the preparation method of the odorless resin provided by the present invention is excellent in properties such as fineness, hydroxyl value, viscosity, solid content, appearance, and acid value.

Application example

The application examples were prepared from example 1, example 3, and example 5, and commercially available toplift 3871 (available from shenzhen, toplift polo technologies ltd) and properzem 9855 (available from foshan properzem resins ltd) as raw material resins, respectively, to form varnishes nos. 1 to 5, wherein the varnish composition ratios are shown in table 3.

Table 3 the varnish composition ratios in mass percent.

And then, respectively carrying out primary spraying and secondary spraying on the paint preparation spraying plate by using No. 1-No. 5 spraying of the varnish, and characterizing.

Primary spraying:

the method comprises the following steps: the varnish No. 1 to No. 5 is respectively used as a raw material, the varnish No. 1 to No. 5 is sprayed to prepare a paint spraying plate (the prepared paint spraying plate meets the requirements of national standard document 'colored paint and varnish standard test plate' with the number of GBT 9271-1988), the size of the prepared paint spraying plate is 60cm multiplied by 60cm, the spraying method is to carry out two times of cross spraying, namely 4 times of spraying, and the performance of the prepared paint spraying plate is shown in Table 4.

Wherein:

the "appearance" was tested by the method provided in the national standard document "determination of appearance and transparency of varnishes, varnishes and diluents" with reference number GB 1721-1979.

The test is carried out by the method provided by the national standard document 'determination method of drying time of paint film and putty film' with the reference number of GB/T1728-1989.

"flexibility" is tested by the method provided in the national Standard document putty film flexibility assay, GB/T1748-1989.

The adhesion is tested by the method provided in the national standard document paint adhesion determination of GB/T1720-1989.

Table 4 properties of the painted panels after one spray.

Test item	Number 1	Number 2	No. 3	Number 4	Number 5
						Dried bean curd	38 minutes in 1 hour	1 hour and 35 minutes	1 hour and 30 minutes	1 hour and 30 minutes	1 hour 45 minutes
Levelling	You Luo	Superior food	Good and good wine	Superior food	You Luo
						Flexibility 12h	4 stage	Grade 5	Grade 5	5 grade-	Grade 5
Filling property	Liang nationality	Liang nationality	Good materials	Difference (D)	Good materials
						Fullness degree	You Luo	Superior food	You Luo	Good and good wine	Superior food
Gloss (4h)	65	64	65	62	67
						Gloss (24)h)	61	60	59	45	51
Transparency	Superior food	Superior food	Good and good wine	Good wine	Liang nationality

Secondary spraying:

and respectively spraying No. 1-5 varnish on the No. 1-5 paint-prepared spraying plate after one-time spraying, wherein the spraying method comprises the following steps: each paint distribution spray plate is divided into two parts, one part is subjected to cross re-spraying for 1.5 times (namely, spraying for 3 times), and the other part is subjected to cross re-spraying for 3 times (namely, spraying for 6 times). The characterization of the properties of the painted panels after the second spraying is shown in table 5.

Table 5 properties of the painted panels after the second spraying.

The results in tables 4 to 5 show that the varnish prepared from the odorless resin provided by the invention has a good plate surface effect, has excellent transparency on the premise of ensuring the fullness and adhesion of a paint film, has a more obvious advantage of high transparency under the condition of recoating or thick coating, and well meets the requirement of a high-transparency coating process for high-grade furniture.

The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.