Environment-friendly plant-based functional resin and preparation method of putty powder thereof

Abstract

The invention relates to the technical field of unsaturated polyester putty, and discloses a preparation method of environment-friendly plant-based functional resin and putty powder.The preparation method comprises the steps that 100 parts by weight of unsaturated polyester resin, 8-11 parts by weight of diluent, 5-15 parts by weight of DOPO abietate-based starch, 20-28 parts by weight of calcium carbonate and 30-45 parts by weight of filler are stirred, mixed and ground, and the putty powder is obtained; the environment-friendly plant-based functional resin is obtained. The DOPO abietate-based starch is uniformly dispersed in an unsaturated polyester resin matrix, so that the water resistance and heat resistance of a resin paint film are improved. The DOPO abietate-based starch contains a phosphaphenanthrene flame-retardant structure, the starch is promoted to be dehydrated into carbon during combustion, a carbon barrier layer is formed on the surface of a paint film, a very good flame-retardant effect is achieved, and the obtained resin material has very good practical application in the fields of high-performance putty powder, coatings and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of unsaturated polyester putty, and specifically to a preparation method of an environmentally friendly plant-based functional resin and its putty powder. Background Art

[0002] Unsaturated polyester is a thermosetting resin with excellent performance, having good mechanical properties, dielectric properties, and anti-corrosion properties, and is widely used in building materials such as putty powder, coatings, and artificial stone. Traditional unsaturated polyester has problems such as poor flame retardancy and heat resistance. Improving the water resistance, heat resistance, flame retardancy, etc. of unsaturated polyester is beneficial to expanding its practical applications in high-performance coatings, putty powder and other fields.

[0003] In recent years, the development of green and environmentally friendly biomass resources has been a research hotspot. Starch is cheap, easy to obtain, green and pollution-free, and has excellent bonding properties, and is widely used in putty powder, adhesives, etc. Rosin acid is mainly derived from pine trees, is a natural and environmentally friendly biomass compound, has strong heat resistance and high water resistance, and is widely used. Chinese patent application document CN118496427A discloses a heat-resistant and flame-retardant unsaturated polyester resin and its preparation method, in which a saturated dibasic acid, maleic anhydride, maleopimaric acid, diol, organosilicon prepolymer, etc. are subjected to a polymerization reaction, and the obtained unsaturated polyester resin has good flame retardancy, heat resistance, corrosion resistance and other properties. However, this patent does not improve the water resistance and other properties of the unsaturated polyester resin. Summary of the Invention

[0004] The technical problem solved by the present invention is: solving the problems of poor water resistance, heat resistance and poor flame retardancy of unsaturated polyester resin and its putty powder.

[0005] The technical solution of the present invention: A preparation method of an environmentally friendly plant-based functional resin: Add 100 parts by weight of unsaturated polyester resin, 8 - 11 parts by weight of diluent, 1.2 - 1.8 parts by weight of cobalt promoter, 0.15 - 0.3 parts by weight of amine promoter, 0.002 - 0.005 parts by weight of inhibitor, 5 - 15 parts by weight of DOPO rosin acid ester-based starch into a mixer and stir evenly, then add 20 - 28 parts by weight of calcium carbonate and 30 - 45 parts by weight of filler, stir and then grind through a grinder, and discharge to obtain an environmentally friendly plant-based functional resin.

[0006] Further, the diluent is styrene.

[0007] Further, the cobalt promoter is cobalt naphthenate.

[0008] Further, the inhibitor is hydroquinone.

[0009] Further, the amine accelerator is N,N-dimethylaniline, N-methyl-N-hydroxyethyl-p-toluidine or N,N-dimethyl-p-toluidine.

[0010] Further, the filler is any one or combination of talcum powder, titanium dioxide and diatomite.

[0011] Further, the preparation method of DOPO rosin acid ester-based starch is as follows:

[0012] (1) Add 100 parts by weight of glycidyl rosinate, 220 - 260 parts by weight of DOPO-maleic acid and 4 - 5 parts by weight of catalyst to toluene, heat to 100 - 120 °C, carry out condensation reflux reaction for 7 - 10 h, carry out vacuum distillation, wash with water and ethanol, and recrystallize the product in toluene to obtain the DOPO rosin acid ester intermediate.

[0013] The reaction formula is:

[0014]

[0015] (2) Add 100 parts by weight of carboxymethyl starch to dimethyl sulfoxide, after heating and stirring, add 80 - 200 parts by weight of DOPO rosin acid ester intermediate, 3 - 8 parts by weight of 4-dimethylaminopyridine and 16 - 42 parts by weight of N,N-dicyclohexylcarbodiimide, carry out stirring reaction at 20 - 35 °C for 24 - 36 h, pour the solution into ethanol for precipitation, filter and wash successively with water and ethanol, and dry to obtain DOPO rosin acid ester-based starch.

[0016] The reaction formula is:

[0017]

[0018] Further, the catalyst in (1) is tetrabutylammonium bromide or benzyltriethylammonium chloride.

[0019] Further, the environment-friendly plant-based functional resin is applied to putty powder.

[0020] The technical effect of the present invention: In the present invention, glycidyl rosinate and DOPO-maleic acid are subjected to epoxy ring-opening reaction to obtain the DOPO rosin acid ester intermediate, the hydroxyl group thereof undergoes esterification reaction with the carboxyl group of carboxymethyl starch to obtain DOPO rosin acid ester-based starch, and then it is blended with unsaturated polyester resin, styrene diluent, accelerator, filler, etc. to obtain the environment-friendly plant-based functional resin material.

[0021] The DOPO rosin acid ester-based starch of the present invention contains a hydrophobic rosin condensed ring and a benzene ring structure, which can improve the hydrophobicity of the starch, is beneficial to improving the water resistance of the paint film. At the same time, the rosin condensed ring contained in the starch has strong heat resistance and is not easily thermally decomposed, which can improve the heat resistance of the paint film. The DOPO rosin acid ester intermediate itself contains a large number of ester groups. After undergoing an esterification reaction with the carboxyl groups of carboxymethyl starch, the starch contains a large number of ester group groups identical to those of unsaturated polyester resin, significantly improving the polarity between the starch and the polyester resin, and making their compatibility better. As a result, the DOPO rosin acid ester-based starch is uniformly dispersed in the unsaturated polyester resin matrix, and there will be no interfacial defects and phase separation phenomena due to poor compatibility between the two. After the water resistance and heat resistance tests, the paint film is complete, without bubbling, wrinkling, or cracking.

[0022] The DOPO rosin acid ester-based starch of the present invention contains a DOPO phosphaphenanthrene flame retardant structure grafted into the starch matrix. During combustion, the DOPO structure pyrolyzes to produce phosphoric acid substances, which can quickly contact the starch, promote the dehydration and carbonization of the starch, form a carbon barrier layer on the surface of the paint film, achieve a good flame retardant effect, significantly improve the limiting oxygen index of the paint film, and the UL94 rating reaches V-1 to V-0 grades. The obtained resin material has good practical applications in high-performance putty powder, coatings and other fields. Detailed implementation mode

[0023] The following unsaturated polyester resin with an effective ingredient content of 99% was purchased from Jinan Dayang New Material Technology Co., Ltd. Carboxymethyl starch and starch were purchased from Xi'an Qingyan Biotechnology Co., Ltd.

[0024] Prepare rosin glycidyl ester according to the method in the journal "Journal of Fuzhou University (Natural Science Edition), Vol. 30, No. 6, December 2002, the literature "Preparation of Rosin Glycidyl Ester and Its Application in Polyester Synthesis". The structural formula is

[0025] Prepare DOPO-maleic acid according to the method in the journal "Synthetic Resin and Plastics", 2015, 32(3): 35, the literature "Synthesis of Reactive Flame Retardant DOPO-Maleic Acid and Its Flame Retardant Research on Alkyd Resin".

[0026] The structural formula is

[0027] Example 1:

[0028] (1) Add 5 g of rosin glycidyl ester, 11 g of DOPO-maleic acid, and 0.25 g of tetrabutylammonium bromide to 130 mL of toluene, heat to 100 °C, carry out a reflux reaction for 10 h, distill under reduced pressure, wash with water and ethanol, and recrystallize the product from toluene to obtain the DOPO rosin acid ester intermediate.

[0029] (2) Add 30 g of carboxymethyl starch to 800 mL of dimethyl sulfoxide, heat to 90 °C and stir for 40 min. Add 24 g of DOPO rosin acid ester intermediate, 0.9 g of 4-dimethylaminopyridine, and 4.8 g of N,N'-dicyclohexylcarbodiimide. Stir and react at 25 °C for 24 h. Pour the solution into ethanol for precipitation, filter, wash successively with water and ethanol, and dry to obtain DOPO rosin acid ester-based starch.

[0030] (3) Add 1 kg of unsaturated polyester resin, 92 g of styrene, 13.8 g of cobalt naphthenate, 2.2 g of N,N-dimethylaniline, 0.04 g of inhibitor hydroquinone, and 50 g of DOPO rosin acid ester-based starch to a mixer and stir to mix evenly. Then add 220 g of calcium carbonate, 320 g of talc powder, 56 g of titanium dioxide, and 24 g of diatomaceous earth. After stirring, grind through a grinder and discharge to obtain an environmentally friendly plant-based functional resin.

[0031] Example 2:

[0032] (1) Add 5 g of glycidyl rosinate, 13 g of DOPO-maleic acid, and 0.2 g of benzyltriethylammonium chloride to 120 mL of toluene. Heat to 120 °C and carry out a condensation reflux reaction for 7 h. Carry out vacuum distillation, wash with water and ethanol, and recrystallize the product from toluene to obtain DOPO rosin acid ester intermediate.

[0033] (2) Add 30 g of carboxymethyl starch to 800 mL of dimethyl sulfoxide, heat to 90 °C and stir for 40 min. Add 40 g of DOPO rosin acid ester intermediate, 1.6 g of 4-dimethylaminopyridine, and 8.1 g of N,N'-dicyclohexylcarbodiimide. Stir and react at 35 °C for 24 h. Pour the solution into ethanol for precipitation, filter, wash successively with water and ethanol, and dry to obtain DOPO rosin acid ester-based starch.

[0034] (3) Add 1 kg of unsaturated polyester resin, 110 g of styrene, 18 g of cobalt naphthenate, 1.5 g of N,N-dimethyl-p-toluidine, 0.05 g of inhibitor hydroquinone, and 100 g of DOPO rosin acid ester-based starch to a mixer and stir to mix evenly. Then add 280 g of calcium carbonate, 230 g of talc powder, 43 g of titanium dioxide, and 27 g of diatomaceous earth. After stirring, grind through a grinder and discharge to obtain an environmentally friendly plant-based functional resin.

[0035] Example 3:

[0036] (1) Add 30 g of carboxymethyl starch to 900 mL of dimethyl sulfoxide, heat to 90 °C and stir for 40 min. Add 60 g of DOPO rosin acid ester intermediate (prepared according to the method of Example 1), 2.4 g of 4-dimethylaminopyridine, and 12.6 g of N,N-dicyclohexylcarbodiimide. Stir and react at 20 °C for 36 h. Pour the solution into ethanol for precipitation. After filtration, wash with water and ethanol in sequence, and dry to obtain DOPO rosin acid ester-based starch.

[0037] (2) Add 1 kg of unsaturated polyester resin, 80 g of styrene, 12 g of cobalt naphthenate, 3 g of N-methyl-N-hydroxyethyl-p-toluidine, 0.02 g of inhibitor hydroquinone, and 150 g of DOPO rosin acid ester-based starch into a mixer and stir evenly. Then add 200 g of calcium carbonate, 340 g of talc powder, 65 g of titanium dioxide, and 45 g of diatomaceous earth. After stirring, grind through a grinder and discharge to obtain an environmentally friendly plant-based functional resin.

[0038] Comparative Example 1:

[0039] (1) Add 1 kg of unsaturated polyester resin, 92 g of styrene, 13.8 g of cobalt naphthenate, 2.2 g of N,N-dimethylaniline, 0.04 g of inhibitor hydroquinone, and 50 g of carboxymethyl starch into a mixer and stir evenly. Then add 220 g of calcium carbonate, 320 g of talc powder, 56 g of titanium dioxide, and 24 g of diatomaceous earth. After stirring, grind through a grinder and discharge to obtain an environmentally friendly plant-based functional resin.

[0040] Comparative Example 2:

[0041] (1) Stir and blend 30 g of carboxymethyl starch and 24 g of DOPO rosin acid ester intermediate to obtain a DOPO rosin acid ester intermediate-starch blend.

[0042] (2) Add 1 kg of unsaturated polyester resin, 92 g of styrene, 13.8 g of cobalt naphthenate, 2.2 g of N,N-dimethylaniline, 0.04 g of inhibitor hydroquinone, and 50 g of DOPO rosin acid ester intermediate-starch blend into a mixer and stir evenly. Then add 220 g of calcium carbonate, 320 g of talc powder, 56 g of titanium dioxide, and 24 g of diatomaceous earth. After stirring, grind through a grinder and discharge to obtain an environmentally friendly plant-based functional resin.

[0043] Comparative Example 3:

[0044] (1) Add 30 g of starch to 800 mL of dimethyl sulfoxide, heat to 90 °C and stir for 40 min. Then add 24 g of DOPO-maleic acid, 0.9 g of 4-dimethylaminopyridine, and 4.8 g of N,N'-dicyclohexylcarbodiimide. Stir and react at 25 °C for 24 h. Pour the solution into ethanol for precipitation, filter, wash successively with water and ethanol, and dry to obtain DOPO-based starch.

[0045] (2) Add 1 kg of unsaturated polyester resin, 92 g of styrene, 13.8 g of cobalt naphthenate, 2.2 g of N,N-dimethylaniline, 0.04 g of inhibitor hydroquinone, and 50 g of DOPO-based starch to a mixer and stir to mix evenly. Then add 220 g of calcium carbonate, 320 g of talc powder, 56 g of titanium dioxide, and 24 g of diatomaceous earth. Stir and then grind through a grinder, and discharge to obtain an environmentally friendly plant-based functional resin.

[0046] Comparative Example 4:

[0047] (1) Add 30 g of carboxymethyl starch to 800 mL of dimethyl sulfoxide, heat to 90 °C and stir for 40 min. Then add 24 g of rosin acid, 0.9 g of 4-dimethylaminopyridine, and 4.8 g of N,N'-dicyclohexylcarbodiimide. Stir and react at 25 °C for 24 h. Pour the solution into ethanol for precipitation, filter, wash successively with water and ethanol, and dry to obtain rosin acid-based starch.

[0048] (2) Add 1 kg of unsaturated polyester resin, 92 g of styrene, 13.8 g of cobalt naphthenate, 2.2 g of N,N-dimethylaniline, 0.04 g of inhibitor hydroquinone, and 50 g of rosin acid-based starch to a mixer and stir to mix evenly. Then add 220 g of calcium carbonate, 320 g of talc powder, 56 g of titanium dioxide, and 24 g of diatomaceous earth. Stir and then grind through a grinder, and discharge to obtain an environmentally friendly plant-based functional resin.

[0049] Cure the putty powder at 80 °C for 3 h and then at 100 °C for 2 h to form a paint film.

[0050] Test the water resistance of the paint film according to the method of GB / T 1733-1993. Test the water resistance of the paint film according to the method of GB / T 1735-1979.

[0051] Test the oxygen index and flame retardancy according to the method of GB / T 2406.1-2008. Test the vertical burning performance according to the UL94 method.

[0052] Table 1 Performance Test of Functional Resin

[0053]

[0054]

[0055] After testing, compared with Comparative Example 1, DOPO rosin acid ester-based starch is added to the unsaturated polyester resins of Examples 1-3. The DOPO rosin acid ester-based starch contains a hydrophobic rosin condensed ring and a benzene ring structure, which can improve the hydrophobicity of the starch, is beneficial to improving the water resistance of the paint film. At the same time, the rosin condensed ring contained in the starch has strong heat resistance and is not easily thermally decomposed, which can improve the heat resistance of the paint film. And the DOPO rosin acid ester intermediate itself contains a large number of ester groups. After esterification reaction with the carboxyl groups of carboxymethyl starch, the starch contains a large number of ester group groups identical to those of the unsaturated polyester resin, significantly improving the polarity between the starch and the polyester resin, and the compatibility between the two is better, making the DOPO rosin acid ester-based starch evenly dispersed in the unsaturated polyester resin matrix, and no interface defects and phase separation phenomena will occur between the two due to poor compatibility. After the water resistance and heat resistance tests, the paint film is intact, without bubbling, wrinkling or cracking. And the DOPO rosin acid ester-based starch contains a DOPO phosphaphenanthrene flame retardant structure. Grafted into the starch matrix, when burning, the DOPO structure pyrolyzes to produce phosphoric acid substances, which can quickly contact with the starch, promote the dehydration and carbonization of the starch, form a carbon barrier layer on the surface of the paint film, play a good flame retardant effect, significantly improve the limiting oxygen index of the paint film, and the UL94 rating reaches V-1 to V-0 levels.

[0056] Comparative Example 2 added a blend of DOPO rosin acid ester intermediate and starch. The starch has a large hydrophilicity, which is not conducive to improving the water resistance of the paint film. And the compatibility between the starch and the unsaturated polyester resin is poor, and interface defects and phase separation phenomena are likely to occur between the starch and the polyester resin. After the water resistance and heat resistance tests, the paint film is prone to bubbling and wrinkling.

[0057] In Comparative Example 3, the esterification reaction was carried out between the hydroxyl group of starch and the carboxyl group of DOPO-maleic acid. The starch contains fewer ester groups, and its compatibility with the unsaturated polyester resin is lower than that of Example 1, and it does not contain a hydrophobic and heat-resistant rosin condensed ring structure. After the water resistance and heat resistance tests, the paint film is prone to bubbling and cracking.

[0058] In Comparative Example 4, the esterification reaction was carried out between the hydroxyl group of starch and the carboxyl group of rosin acid. The starch contains fewer ester groups, and its compatibility with the unsaturated polyester resin is lower than that of Example 1, and it does not contain a hydrophobic benzene ring and a flame-retardant DOPO phosphaphenanthrene structure. After the water resistance and heat resistance tests, the paint film is prone to bubbling and cracking, and at the same time, the flame retardancy of the paint film is poor.

Claims

1. A method for preparing an environmentally friendly plant-based functional resin, characterized in that: The preparation method comprises: adding 100 parts by weight of unsaturated polyester resin, 8-11 parts by weight of diluent, 1.2-1.8 parts by weight of cobalt accelerator, 0.15-0.3 parts by weight of amine accelerator, 0.002-0.005 parts by weight of polymerization inhibitor, and 5-15 parts by weight of DOPO rosin acid ester-based starch into a mixer, stirring and mixing, then adding 20-28 parts by weight of calcium carbonate and 30-45 parts by weight of filler, stirring, grinding with a grinder, discharging, and obtaining an environmentally friendly plant-based functional resin; The preparation method of the DOPO rosin acid ester starch comprises: adding carboxymethyl starch to dimethyl sulfoxide, adding DOPO rosin acid ester intermediate, 4-dimethylaminopyridine and N,N-dicyclohexylcarbodiimide after heating and stirring, pouring the solution into ethanol for precipitation after reaction, filtering, washing and drying to obtain the DOPO rosin acid ester starch.

2. The method for preparing the environmentally friendly plant-based functional resin according to claim 1, characterized in that: The diluent is styrene, the cobalt accelerator is cobalt cyclohexaneate, and the inhibitor is hydroquinone.

3. The method for preparing the environmentally friendly plant-based functional resin according to claim 1, characterized in that: The amine accelerator is N,N-dimethylaniline, N-methyl-N-hydroxyethyl-p-methylaniline or N,N-dimethyl-p-toluidine.

4. The method for preparing the environmentally friendly plant-based functional resin according to claim 1, characterized in that: The filler is any one or a combination of talc, titanium dioxide and diatomaceous earth.

5. The method for preparing the environmentally friendly plant-based functional resin according to claim 1, characterized in that: The reaction temperature is 20-35°C and the reaction time is 24-36h.

6. The method for preparing the environmentally friendly plant-based functional resin according to claim 1, characterized in that: The dosage of the carboxymethyl starch is 100 parts by weight, the DOPO rosin acid ester intermediate is 80-200 parts by weight, the 4-dimethylaminopyridine is 3-8 parts by weight, and the N,N-dicyclohexylcarbodiimide is 16-42 parts by weight.

7. The method for preparing the environmentally friendly plant-based functional resin according to claim 6, characterized in that: The preparation method of the DOPO rosin acid ester intermediate is as follows: add rosin glycidyl ester, DOPO-maleic acid and a catalyst into toluene, heat to 100-120° C., react for 7-10 hours, perform vacuum distillation, wash and recrystallize the product to obtain the DOPO rosin acid ester intermediate.

8. The method for preparing the environmentally friendly plant-based functional resin according to claim 7, characterized in that: The dosage of the DOPO-maleic acid is 100 parts by weight, the dosage of the rosin glycidyl ester is 220-260 parts by weight, and the dosage of the catalyst is 4-5 parts by weight.

9. The method for preparing the environmentally friendly plant-based functional resin according to claim 8, characterized in that: The catalyst is tetrabutylammonium bromide or benzyltriethylammonium chloride.

10. A putty powder made from an environmentally friendly plant-based functional resin obtained by the preparation method according to any one of claims 1 to 9.

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