A spray-type environmentally friendly elastic putty and preparation method thereof

Abstract

The invention provides a spray-type environmentally friendly elastic putty and a preparation method thereof. The spray-type environmentally friendly elastic putty mainly comprises a highly flexible unsaturated polyester resin, an inorganic filler, a homemade diluent cross-linking agent monomer, cobalt isooctanoate, diphenylmethane diisocyanate, a leveling agent and a catalyst. A preparation method of the spray-type environmentally friendly elastic putty is also provided. The prepared putty product can not only be sprayed to achieve rapid coating operations, but the sprayed putty also has excellent flexibility, adhesion and impact resistance. At the same time, the preparation process of the putty is safe and environmentally friendly, can reduce the volatilization of harmful gases, and reduce the harm to construction personnel. The prepared putty has good polishing properties and is easy to dry, which greatly improves the construction efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of caulking materials, and particularly relates to a spray-type environmentally friendly elastic putty and a preparation method thereof.

Background Art

[0002] Putty is a decorative material for leveling the surface of objects. It is a thick paste-like coating and an essential product before paint brushing. Putty is widely used in various product fields that require filling and repairing, such as the machinery industry, instrument electronics, wooden furniture, and automobile manufacturing, etc., to effectively fill and decorate defects such as pits, pinholes, cracks, and welds on the substrate, and to meet the flatness and smoothness of the substrate surface.

[0003] Currently, the construction of putty is all carried out by scraping, which requires high skills for scraping operators. And before scraping, the main ash and the curing agent must be mixed first. During the mixing process, it is easy to mix in air bubbles, which affects the quality of the subsequent coating film. Styrene is usually used in the preparation of putty. Although styrene can be used as a diluent to reduce the viscosity of the system, styrene has a high volatility. As a toxic and harmful gas, it is easy to volatilize into the air, causing environmental pollution and harm to construction workers. And because styrene is also prone to self-polymerization to form rigid polystyrene chains during the cross-linking and curing process, these rigid molecular chains will reduce the flexibility of the prepared putty, making the material very brittle. In addition, a large amount of fillers are also added in the traditional putty preparation process, which will further sharply reduce the flexibility of the putty, and the impact resistance is poor, and it is easy to be damaged during impact, and the surface is easy to crack.

[0004] Therefore, providing a caulking material solution that can be used by spraying, has excellent flexibility, and is green and environmentally friendly is an urgent problem to be solved at present.

Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a spray-type environmentally friendly elastic putty and a preparation method thereof.

[0006] The technical solution provided by the present invention can, to a certain extent, make up for the defects of the putty provided by the prior art, such as non-sprayability and non-environmental friendliness.

[0007] In order to achieve the above object, it is realized through the following technical solutions:

[0008] A spray-type environmentally friendly elastic putty, characterized in that it includes component A and component B, and the weight ratio of each raw material in component A is:

[0009] High-flexibility unsaturated polyester resin: 30 - 45 parts

[0010] Talcum powder: 25 - 30 parts

[0011] Mica powder: 10 - 25 parts

[0012] Calcium carbonate: 10 - 20 parts

[0013] Titanium dioxide: 5 - 10 parts

[0014] Fumed silica: 1 - 1.5 parts

[0015] Self - made diluted cross - linker monomer: 10 - 15 parts

[0016] Cobalt isooctanoate: 0.1 - 0.5 parts

[0017] Stabilizer: 0.5 - 1 part

[0018] Dispersant: 0.2 - 1.2 parts

[0019] Leveling agent: 0.6 - 1.6 parts

[0020] Catalyst: 0.1 - 0.5 part

[0021] Component B is liquid cyclohexanone peroxide; the mixing weight ratio of Component A to Component B is 100:1.8 - 2.5.

[0022] The preparation process of the spray - type environmental - friendly elastic putty is as follows:

[0023] 1), Weigh each raw material component according to the ratio of Component A above;

[0024] 2), Add the weighed high - flexibility unsaturated polyester resin into the reaction vessel. Under stirring at a speed of 300 - 500 r / min, add the weighed cobalt isooctanoate into the above - mentioned vessel, stir for 10 - 15 min, then add the dispersant and the stabilizer, stir for 10 - 15 min, then add talcum powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst and fumed silica for stirring, dispersing and mixing for 2 - 5 h, then add the diluted cross - linker monomer, and continue to stir for 2 - 5 h until Component A with uniform dispersion and flowing state is obtained; before spraying, Component A and Component B are packaged separately, and when in use, mix Component A and Component B evenly according to the given mixing ratio to obtain the spray - type environmental - friendly elastic putty.

[0025] The preparation process of the high - flexibility unsaturated polyester resin is as follows:

[0026] Add methyl propylene glycol, diethylene glycol, isophthalic acid, tetrahydrophthalic anhydride, and hydroquinone into a reaction vessel, heat it and introduce nitrogen. Raise the reaction temperature to 150 - 160 °C, keep the temperature for 3 - 5 h, then cool it down to 100 - 120 °C. Then add punicic acid, dimer acid, p-phenylenediamine, phthalic anhydride, and diethylene glycol, and raise the temperature to 200 - 210 °C at a rate of 10 - 15 °C / h, keep the temperature for 3 - 5 h, evacuate for 0.5 h. When the acid value is measured to be below 30 - 40 mg KOH / g, cool it down to 100 - 120 °C. Gradually add the self-made diluted crosslinking agent monomer into the reaction vessel under continuous stirring, mix and stir for 3 - 5 h, then add diphenylmethane diisocyanate into the reaction vessel. At the same time, control the temperature of the liquid in the reaction vessel below 60 °C through cooling water. After the temperature of the liquid in the reaction vessel is stable, turn off the cooling water, then add tetrabutyl titanate into the reaction vessel, control the reaction temperature at 50 - 65 °C and react for 3 - 5 hours, and cool it down to obtain a highly flexible unsaturated polyester resin.

[0027] The dosages of each raw material in the preparation of the highly flexible unsaturated polyester are as follows:

[0028] Methyl propylene glycol: 50 - 65 parts, diethylene glycol: 50 - 60 parts, diethylene glycol: 55 - 65 parts, punicic acid: 35 - 40 parts, isophthalic acid: 30 - 35 parts, p-phenylenediamine: 40 - 50 parts, dimer acid: 50 - 60 parts, phthalic anhydride: 40 - 45 parts, tetrahydrophthalic anhydride: 20 - 30 parts, hydroquinone: 1 - 5 parts, self-made diluted crosslinking agent monomer: 80 - 100 parts, tetrabutyl titanate: 1 - 2 parts, diphenylmethane diisocyanate: 70 - 80 parts.

[0029] The self-made diluted crosslinking agent monomer uses a self-made new monomer that can completely replace traditional diluted crosslinking agents such as styrene as the diluted crosslinking agent. The diluted crosslinking agent monomer uses 2-hydroxyethyl acrylate (HEA) and 1,4-cyclohexane-diisocyanate (CHDI) as reaction raw materials, and reacts between the hydroxyl group of HEA and the isocyanate group in CHDI to generate a HEA-CHDI adduct with carbon-carbon double bonds at both ends. The preparation process of the crosslinking diluent is as follows:

[0030] Weigh a certain amount of 2-hydroxyethyl acrylate and 1,4-cyclohexane-diisocyanate and mix them into a flask. The molar ratio of 2-hydroxyethyl acrylate to 1,4-cyclohexane-diisocyanate is 2.1:1. Then add 0.2% of stannous octoate based on the total mass of the above mixture as a catalyst, drive out the air in the flask with argon, heat it to 50 - 60 °C under stirring at 300 r / min, and stir and react for 3 - 5 h to obtain it.

[0031] The reaction route of the above-prepared HEA-CHDI is as follows:

[0032]

[0033] In the preparation process of the present invention, the leveling agent is an acrylate leveling agent, and the stabilizer is one or more of polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol.

[0034] In the preparation process of the present invention, the dispersant is a high molecular weight unsaturated polycarboxylic acid solution of organically modified polysiloxane, and the catalyst is one or more of antimony oxide, zinc acetate and p-toluenesulfonic acid.

[0035] The beneficial effects of the present invention are as follows:

[0036] 1. In the present invention, the high-flexibility unsaturated polyester resin uses dimer acid and punicic acid as toughening raw materials, which are added by in-situ polymerization. Based on the fact that dimer acid and punicic acid contain relatively long flexible methylene chains and relatively rigid cyclic structures in the monocyclic structure, they can toughen the molecular chain segments of the unsaturated polyester resin and enhance the flexibility of the unsaturated polyester resin. However, the mechanical strength performance decreases to some extent. Further, based on the active reactive groups in the dimer acid chain, p-phenylenediamine is added for amidation reaction to modify the unsaturated polyester structure, enhancing the hydrogen bond interaction in the chain segments and making the internal cross-linked network structure more compact, thereby improving the mechanical strength of the prepared putty.

[0037] 2. The present invention uses a self-made HEA-CHDI monomer to replace the volatile and harmful styrene as a diluting cross-linking agent. The relatively high molecular weight and hydrogen bond interaction of the HEA-CHDI monomer will not cause volatilization, greatly reducing the volatilization of organic substances and the pungent odor during the preparation process of the putty, reducing the harm of volatile organic compounds to human health and the environment. Moreover, the side chain groups with high functionality and steric hindrance effects in the diluting cross-linking agent monomer can increase the cross-linking density of the cured system, thereby endowing the putty with excellent hardness and mechanical strength, and the relatively long non-polar carbon chain can reduce the viscosity and cured volume shrinkage rate of the system, and can improve the adhesion of the cured putty.

[0038] 3. Finally, the high-flexibility unsaturated polyester resin of the present invention is blended with diphenylmethane diisocyanate, enabling diphenylmethane diisocyanate to react with the excessive hydroxyl groups in the resin, forming polyurethane segments while increasing the relative molecular weight of the resin, causing microphase separation after the macromolecules are cured, forming alternating segments of toughness and rigidity, increasing the cross-linking degree of the system and the degree of interpenetration of the structure network, thereby endowing the material with higher flexibility. After the polyurethane segments are heated during curing, the chain segments where they are located are easily elongated, thus offsetting the curing shrinkage of the resin and also reducing the shrinkage rate of the resin.

[0039] 4. By reasonably matching the composition and ratio of each raw material, the molecular structure and viscosity of the polyester resin are adjusted, and the original high-viscosity state is modified into a low-viscosity fluid state, effectively ensuring that the prepared putty can be atomized for spraying. Compared with the conventional scraping putty, the spraying putty can complete the coating quickly, and the operation difficulty is reduced. Therefore, the operation efficiency can be significantly improved. At the same time, the quality of the putty film prepared by the present invention is also guaranteed, and it is green and environmentally friendly during the preparation process. The above advantages are conducive to the wide application of this putty.

[0040] Additional aspects and advantages of the present invention will be given in part in the following description, which will become apparent from the following description or be understood through the embodiments of the present invention.

Specific Embodiments

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. Other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.

[0042] In the embodiments of the present invention, by reasonably matching each raw material and rationally proportioning the mass percentages of the components of the spraying-type environmentally friendly elastic putty, the molecular structure and viscosity of the polyester resin are adjusted, and the original high-viscosity state is modified into a low-viscosity fluid state, effectively ensuring that the prepared putty can be atomized for spraying. The putty prepared by the present invention includes components A and B, both of which are in a fluid state. Components A and B can be simultaneously transported to a pump and fed into a spraying machine according to a given weight ratio. After being mixed evenly in the spraying machine, spraying operations can be carried out. Compared with the conventional scraping putty, the spraying putty can complete the coating quickly, and the operation difficulty is reduced. Therefore, the operation efficiency can be significantly improved. At the same time, the quality of the putty film prepared by the present invention is also guaranteed. Compared with the traditional scraping putty, the putty system prepared by the present invention has excellent stability and mechanical properties, is easy to polish, and has obvious powdering. It is green and environmentally friendly during the putty preparation process. The above advantages are conducive to the wide application of this putty.

[0043] In some embodiments, the preparation process of the high-flexibility unsaturated polyester resin is as follows:

[0044] Add methyl propylene glycol, diethylene glycol, isophthalic acid, tetrahydrophthalic anhydride, and hydroquinone into a reaction vessel, heat it and introduce nitrogen. Raise the reaction temperature to 150 - 160 °C, keep the temperature for 3 - 5 h, then cool it down to 100 - 120 °C. Then add punicic acid, dimer acid, p-phenylenediamine, phthalic anhydride, and diethylene glycol, and raise the temperature to 200 - 210 °C at a rate of 10 - 15 °C / h, keep the temperature for 3 - 5 h, evacuate for 0.5 h. When the acid value is below 30 - 40 mg KOH / g, cool it down to 100 - 120 °C. Gradually add a diluted crosslinking agent monomer to the reaction vessel under continuous stirring, mix and stir for 3 - 5 h, then add diphenylmethane diisocyanate to the reaction vessel. At the same time, control the temperature of the liquid in the reaction vessel to be below 60 °C through cooling water. After the temperature of the liquid in the reaction vessel is stable, turn off the cooling water. Then add tetrabutyl titanate to the reaction vessel, control the reaction temperature at 50 - 65 °C for 3 - 5 hours, and cool it down to obtain a highly flexible unsaturated polyester resin.

[0045] The dosages of each raw material in the preparation of the highly flexible unsaturated polyester are as follows:

[0046] Methyl propylene glycol: 50 - 65 parts, diethylene glycol: 50 - 60 parts, diethylene glycol: 55 - 65 parts, punicic acid: 35 - 40 parts, isophthalic acid: 30 - 35 parts, p-phenylenediamine: 40 - 50 parts, dimer acid: 50 - 60 parts, phthalic anhydride: 40 - 45 parts, tetrahydrophthalic anhydride: 20 - 30 parts, hydroquinone: 1 - 5 parts, diluted crosslinking agent: 80 - 100 parts, tetrabutyl titanate: 1 - 2 parts, diphenylmethane diisocyanate: 70 - 80 parts.

[0047] In some embodiments, the preparation process of the self-made crosslinking diluent monomer is as follows:

[0048] Weigh a certain amount of 2-hydroxyethyl acrylate and 1,4-cyclohexane-diisocyanate and mix them into a flask. The molar ratio of 2-hydroxyethyl acrylate to 1,4-cyclohexane-diisocyanate is 2.1:1. Then add stannous octoate accounting for 0.2% of the total mass of the above mixture as a catalyst, drive out the air in the flask with argon, heat it to 50 - 60 °C under stirring at 300 r / min, and stir and react for 3 - 5 h to obtain it.

[0049] The raw materials used in the examples and comparative examples of the present invention are all commercially available conventional industrial products.

[0050] Example 1:

[0051] A spray-type environmentally friendly elastic putty, characterized in that it includes component A and component B, and the weight ratio of each raw material in component A is:

[0052] Highly flexible unsaturated polyester resin: 35 parts

[0053] Talcum powder: 25 parts

[0054] Mica powder: 15 parts

[0055] Calcium carbonate: 10 parts

[0056] Titanium dioxide: 8 parts

[0057] Fumed silica: 1 part

[0058] Self-made diluted crosslinking monomer: 15 parts

[0059] Cobalt isooctanoate: 0.3 part

[0060] Stabilizer: 0.5 part

[0061] Dispersant: 0.5 part

[0062] Leveling agent: 1 part

[0063] Catalyst: 0.2;

[0064] Component B is liquid cyclohexanone peroxide; the mixing weight ratio of component A to component B is 100:2.

[0065] The preparation process of the spray-type environmental protection elastic putty is as follows:

[0066] 1), Weigh each raw material component according to the ratio of component A above;

[0067] 2), Add the weighed highly flexible unsaturated polyester resin into the reaction vessel. While stirring at a speed of 500 r / min, add the weighed cobalt isooctanoate into the above-mentioned vessel, stir for 15 min, then add the dispersant and the stabilizer, stir for 10 min, then add talcum powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst and fumed silica and stir and disperse and mix for 5 h, then add the self-made diluted crosslinking monomer, and continue to stir for 5 h until a uniformly dispersed and flowing component A is obtained; before spraying, package component A and component B separately, and when in use, mix component A and component B evenly according to the given mixing ratio to obtain the spray-type environmental protection elastic putty.

[0068] Example 2:

[0069] A spray-type environmental protection elastic putty, characterized in that it includes component A and component B, and the weight ratio of each raw material in component A is:

[0070] Highly flexible unsaturated polyester resin: 45 parts

[0071] Talcum powder: 30 parts

[0072] Mica powder: 10 parts

[0073] Calcium carbonate: 20 parts

[0074] Titanium dioxide: 5 parts

[0075] Fumed silica: 1 part

[0076] Self-made diluted crosslinking agent monomer: 12 parts

[0077] Cobalt isooctanoate: 0.3 part

[0078] Stabilizer: 0.5 part

[0079] Dispersant: 0.2 part

[0080] Leveling agent: 0.6 part

[0081] Catalyst: 0.1 part;

[0082] Component B is liquid cyclohexanone peroxide; the mixing weight ratio of component A to component B is 100:2.2.

[0083] The preparation process of the spray-type environment-friendly elastic putty is as follows:

[0084] 1), Weigh each raw material component according to the ratio of component A above;

[0085] 2), Add the weighed highly flexible unsaturated polyester resin into the reaction vessel, add the weighed cobalt isooctanoate into the above vessel under stirring at a speed of 400 r / min, stir for 10 - 15 min, then add the dispersant and the stabilizer, stir for 15 min, then add talcum powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst, fumed silica and stir and disperse and mix for 2 h, then add the diluted crosslinking agent monomer, and continue to stir for 4 h until a uniformly dispersed and flowing component A is obtained; before spraying, component A and component B are packaged separately, and when in use, mix component A and component B evenly according to the given mixing ratio to obtain the spray-type environment-friendly elastic putty.

[0086] Example 3

[0087] A spray-type environment-friendly elastic putty, characterized in that it includes component A and component B, and the weight ratio of each raw material in component A is:

[0088] Highly flexible unsaturated polyester resin: 40 parts

[0089] Talcum powder: 25 parts

[0090] Mica powder: 20 parts

[0091] Calcium carbonate: 15 parts

[0092] Titanium dioxide: 6 parts

[0093] Fumed silica: 1.2 parts

[0094] Self-made diluted crosslinking monomer: 15 parts

[0095] Cobalt isooctanoate: 0.2 part

[0096] Stabilizer: 0.5 part

[0097] Dispersant: 0.8 part

[0098] Leveling agent: 1.3 parts

[0099] Catalyst: 0.1 part;

[0100] Component B is liquid cyclohexanone peroxide; the mixing weight ratio of component A to component B is 100:1.9.

[0101] The preparation process of the spray-type environment-friendly elastic putty is as follows:

[0102] 1), Weigh each raw material component according to the ratio of component A above;

[0103] 2), Add the weighed highly flexible unsaturated polyester resin into the reaction vessel. Under stirring at a speed of 450 r / min, add the weighed cobalt isooctanoate into the above-mentioned vessel, stir for 15 min, then add the dispersant and stabilizer, stir for 15 min, then add talcum powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst and fumed silica and stir and disperse and mix for 4 h, then add the diluted crosslinking monomer, and continue to stir for 5 h until a uniformly dispersed and flowing component A is obtained; before spraying, package component A and component B separately, and when in use, mix component A and component B evenly according to the given mixing ratio to obtain the spray-type environment-friendly elastic putty.

[0104] Comparative Example 1

[0105] A spray-type environment-friendly elastic putty, characterized in that it includes component A and component B, and the weight ratio of each raw material in component A is:

[0106] Highly flexible unsaturated polyester resin: 40 parts

[0107] Talcum powder: 25 parts

[0108] Mica powder: 20 parts

[0109] Calcium carbonate: 15 parts

[0110] Titanium dioxide: 6 parts

[0111] Fumed silica: 1.2 parts

[0112] 2-Hydroxyethyl acrylate: 15 parts

[0113] Cobalt isooctanoate: 0.2 part

[0114] Stabilizer: 0.5 parts

[0115] Dispersant: 0.8 parts

[0116] Leveling agent: 1.3 parts

[0117] Catalyst: 0.1 part;

[0118] Component B is liquid cyclohexanone peroxide; the mixing weight ratio of Component A to Component B is 100:1.9.

[0119] The preparation process of the spray-type environmentally friendly elastic putty is as follows:

[0120] 1), Weigh each raw material component according to the ratio of Component A above;

[0121] 2), Add the weighed highly flexible unsaturated polyester resin into the reaction vessel. Under stirring at a speed of 450 r / min, add the weighed cobalt isooctanoate into the above-mentioned vessel, stir for 15 min, then add the dispersant and stabilizer, stir for 15 min, then add talc powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst and fumed silica and stir and disperse and mix for 4 h, then add the dilution crosslinking agent, and continue to stir for 5 h until Component A with uniform dispersion and flowing state is obtained; before spraying, Component A and Component B are packaged separately, and when in use, mix Component A and Component B evenly according to the given mixing ratio to obtain the spray-type environmentally friendly elastic putty. The dilution crosslinking agents used in the preparation process are all commercially available 2-hydroxyethyl acrylate.

[0122] Comparative Example 2:

[0123] As a comparative example of the present invention, the difference between Comparative Example 2 and Example 2 is that the preparation process of the unsaturated polyester resin is different, and the rest of the steps are the same. The preparation process of the unsaturated polyester resin in Comparative Example 2 is as follows: Add methylpropanediol, diethylene glycol, isophthalic acid, and tetrahydrophthalic anhydride, hydroquinone into the reaction vessel, heat it and introduce nitrogen, raise the reaction temperature to 150 °C, keep it warm for 5 h, then cool it down to 100 °C, then add phthalic anhydride and diglycol and raise the temperature to 200 °C at a rate of 10 °C / h, keep it warm for 5 h, evacuate for 0.5 h, when the acid value is measured to be below 40 mg KOH / g, cool it down to 100 °C, and gradually add the dilution crosslinking agent monomer into the reaction vessel under continuous stirring. After mixing and stirring for 5 h, then add diphenylmethane diisocyanate into the reaction vessel, and at the same time control the temperature of the liquid in the reaction vessel to be lower than 60 °C through cooling water. After the temperature of the liquid in the reaction vessel is stable, turn off the cooling water, then add tetrabutyl titanate into the reaction vessel, control the reaction temperature to be 50 - 65 °C and react for 3 - 5 hours, and then cool it down to obtain.

[0124] Comparative Example 3:

[0125] As a comparative example of the present invention, Comparative Example 3 is different from Example 1 in that the preparation process of the unsaturated polyester resin is different, and the remaining steps are the same. The preparation process of the unsaturated polyester resin in Comparative Example 3 is as follows: Add methylpropanediol, diethylene glycol, isophthalic acid, tetrahydrophthalic anhydride, and hydroquinone into the reaction vessel, heat it and introduce nitrogen, raise the reaction temperature to 150 °C, keep it warm for 5 h, then cool it down to 120 °C, and then add punicic acid, dimer acid, p-phenylenediamine, phthalic anhydride, and diglycol. Then raise the temperature to 210 °C at a rate of 15 °C / h, keep it warm for 3 h, evacuate for 0.5 h. When the acid value is measured to be below 40 mg KOH / g, cool it down to 100 - 120 °C. The diluent crosslinking monomer is gradually added to the reaction vessel under continuous stirring, and after mixing and stirring for 3 - 5 h, cool it down to obtain the unsaturated polyester resin.

[0126] The putties prepared in Examples 1 - 3 were subjected to performance tests, and the test results are shown in the following table:

[0127] Three samples each of Examples 1 - 3 and Comparative Examples 1 - 3 were taken for performance testing. The performance indicators are shown in Table 1, and the obtained results were averaged, as shown in Table 2 below.

[0128] Table 1 Performance Testing Indicators and Bases

[0129]

[0130] Table 2 Performance Testing Results of the Products

[0131]

[0132]

[0133] As can be seen from the test results in Table 1 above, through the synergistic effect among the components, the putty products prepared in Examples 1 - 3 of the present application enable the finally formed paint film to have excellent flexibility, adhesion, and impact strength. All the above test items are far superior to the requirements of the technical indicators. The prepared putties are all in a fluid state, can be directly fed into the spraying equipment for spraying without multiple batching, can significantly reduce the time-consuming of putty coating, the sprayed putty can closely adhere to the surface of the workpiece with good adhesion, and the surface of the putty film is flat, with a high success rate of one-time spraying and greatly reduced grinding difficulty. Compared with the products in the comparative examples, the products in Examples 1 - 3 have significantly improved indicators such as flexibility, impact resistance, bending property, and adhesion.

[0134] In Comparative Examples 1-3, although some product performance indicators could be maintained qualified, they were far inferior to those of the present invention in terms of impact resistance, adhesion and impact resistance. In Comparative Example 1, 2-hydroxyethyl acrylate was used as a diluting crosslinking agent without modification. Although the putty prepared could reduce the environmental impact caused by styrene volatilization, there was a significant decline in the properties such as the flexibility and adhesion of the putty. It can be seen that by using the self-made diluting crosslinking monomer HEA-CHDI as a diluent and a crosslinking agent, there are side chain groups with high functionality and steric hindrance effects in the diluting crosslinking agent monomer, which can increase the crosslinking density of the cured system, thereby endowing the putty with excellent hardness and mechanical strength, and having a long non-polar carbon chain that can reduce the viscosity and volume shrinkage rate after curing of the system, and can improve the adhesion of the putty after curing; in Comparative Example 2, no toughening raw materials were added during the preparation of unsaturated polyester, and no further modification treatment with p-phenylenediamine was carried out, resulting in a significant decline in the mechanical strength performance of the putty prepared; in Comparative Example 3, diphenylmethane diisocyanate was not added to the prepared unsaturated polyester resin for copolymerization reaction, and the mechanical properties of the obtained putty material were also relatively poor. It can be seen that by carrying out copolymerization with diphenylmethane diisocyanate to form a molecular structure containing a certain amount of polyurethane segments, the flexible and rigid alternating segments in the system are increased, thereby increasing the crosslinking degree of the system, and at the same time enhancing the degree of interpenetration of the structure network, thus endowing the material with higher flexibility and improving the impact resistance of the system.

[0135] The above embodiments merely illustrate the principles and effects of the present invention and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A spray-type environmentally friendly elastic putty, characterized in that: It includes component A and component B, wherein the weight ratio of each raw material in component A is: Highly flexible unsaturated polyester resin: 30-45 parts Talc: 25-30 parts Mica powder: 10-25 parts Calcium carbonate: 10-20 parts Titanium dioxide: 5-10 parts Fumed silica: 1-1.5 parts Homemade diluted crosslinker monomer: 10-15 parts Cobalt 2-octanoate: 0.1-0.5 parts Stabilizer: 0.5-1 part Dispersant: 0.2-1.2 parts Leveling agent: 0.6-1.6 parts Catalyst: 0.1-0.5 parts Component B is cyclohexanone peroxide; the weight ratio of component A to component B is 100:1.8-2.5; The self-made diluent crosslinking agent monomer is prepared by reacting 2-hydroxyethyl acrylate and 1,4-cyclohexane diisocyanate as reaction raw materials under the catalytic action of stannous octoate. The preparation process of the high-flexibility unsaturated polyester resin is as follows: methyl propanediol, diethylene glycol, isophthalic acid, tetrahydrophthalic anhydride, and hydroquinone are added to a reaction container, heated and nitrogen is introduced, the reaction temperature is raised to 150-160°C, kept warm for 3-5h, then cooled to 100-120°C, pomegranate acid, dimer acid, p-phenylenediamine, phthalic anhydride, and ethylene glycol are added, and then the temperature is raised to 200-210°C at a rate of 10-15°C / h, kept warm for 3-5h, vacuumized for 0.5h, and the acid value is 30-40mg. When the concentration of KOH / g is below 100-120°C, the temperature is lowered to 100-120°C, and the self-made diluted crosslinking agent monomer is gradually added to the reaction container under continuous stirring. After mixing and stirring for 3-5 hours, diphenylmethane diisocyanate is added to the reaction container, and the temperature of the liquid in the reaction container is controlled to be lower than 60°C by cooling water. After the temperature of the liquid in the reaction container is stable, the cooling water is turned off, and butyl titanate is added to the reaction container. The reaction temperature is controlled to be 50-65°C for reaction for 3-5 hours, and the temperature is lowered to obtain a highly flexible unsaturated polyester. Resin; the preparation process of the self-made diluent crosslinking agent monomer is as follows: weigh a certain amount of 2-hydroxyethyl acrylate and 1,4-cyclohexane diisocyanate and mix them into a flask, wherein the molar ratio of 2-hydroxyethyl acrylate to 1,4-cyclohexane diisocyanate is 2.1:1, and then add 0.2% of the total mass of the above mixture as a catalyst. Use argon to drive out the air in the bottle, heat to 50-60°C under the stirring condition of 300r / min, and stir the reaction for 3-5h to obtain the obtained product.

2. The putty according to claim 1, characterized in that: The amounts of the raw materials used in preparing the high-flexibility unsaturated polyester are as follows: 50-65 parts of methyl propanediol, 50-60 parts of diethylene glycol, 55-65 parts of ethylene glycol, 35-40 parts of punicic acid, 30-35 parts of isophthalic acid, 40-50 parts of p-phenylenediamine, 50-60 parts of dimer acid, 40-45 parts of phthalic anhydride, 20-30 parts of tetrahydrophthalic anhydride, 1-5 parts of hydroquinone, 80-100 parts of self-made diluent crosslinking agent monomer, 1-2 parts of butyl titanate, and 70-80 parts of diphenylmethane diisocyanate.

3. The putty according to claim 1, characterized in that: The prepared component A is in a flowable state, and the prepared component B is cyclohexanone peroxide in a liquid state.

4. The putty according to claim 1, characterized in that: The leveling agent is an acrylic leveling agent, and the stabilizer is one or more of polyvinyl pyrrolidone, polyvinyl alcohol and polyethylene glycol.

5. The putty according to claim 1, characterized in that: The dispersant is a high molecular weight unsaturated polycarboxylic acid solution of organic modified polysiloxane, and the catalyst is one or more of antimony oxide, zinc acetate, and p-toluenesulfonic acid.

6. A method for preparing the spray-type environmentally friendly elastic putty as claimed in any one of claims 1 to 5, comprising the following steps: 1) Weigh each raw material component according to the ratio of component A; 2) Add the weighed high-flexibility unsaturated polyester resin to the reaction container, add the weighed cobalt isooctanoate to the above container under stirring at a speed of 300-500r / min, stir for 10-15min, then add the dispersant and stabilizer, stir for 10-15min, then add talcum powder, mica powder, calcium carbonate, titanium dioxide, leveling agent, catalyst and fumed silica, stir and disperse and mix for 2-5h, then add the diluted crosslinking agent monomer, and continue stirring for 2-5h until a uniformly dispersed and fluid component A is obtained; Before spraying, the components A and B are packaged separately. When in use, the components A and B are evenly mixed according to a given mixing ratio to obtain a spray-type environmentally friendly elastic putty.

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