CN111995846A - A kind of PTT/artificial granite waste residue composite material and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of polymer materials, and in particular relates to a PTT/artificial granite waste residue composite material and a preparation method thereof. The composite material is prepared from the following raw materials and parts by weight: 100 parts of dimethyl terephthalate, 5-50 parts of artificial granite waste residue, 80-100 parts of propylene glycol, 0.01-0.5 parts of a transesterification catalyst, and 0.01-0.5 parts of a polymerization catalyst share. The composite material prepared by the invention is prepared by melting polycondensation. Due to the low viscosity of the polymerization system and the vigorous mechanical stirring, and the unsaturated resin coated on the surface of the artificial granite waste residue, the artificial granite waste residue is dispersed in the polymerization system. The composite material obtained has excellent comprehensive mechanical properties, and the heat resistance and molding shrinkage rate are obviously improved. More importantly, a PTT/artificial granite waste residue composite material prepared by this method is an in-situ polymerization method that does not require any solvent, and is extremely convenient for industrial production.

Description

A kind of PTT/artificial granite waste residue composite material and preparation method thereof

【Technical field】

The invention belongs to the technical field of material science and relates to a PTT/artificial granite waste residue composite material and a preparation method thereof.

【Background technique】

Artificial granite has the characteristics of bright color, controllable and adjustable color, environmental protection, and can be refurbished many times. It is an internationally popular green environmental protection decorative material. Artificial granite is prepared from heavy calcium powder or sand with different fineness of about 93wt%, unsaturated resin and a small amount of pigments about 7wt%, etc., through vacuum stirring, high pressure vibration, curing and shaping, cutting and grinding. However, in the production process of artificial granite, due to the need to cut and polish the solidified large-size artificial stone, a large amount of waste rock slurry containing calcium carbonate waste residue is generated. The solid waste content in the concentrated solution after precipitation and flocculation is about 20%, this part is called artificial stone waste. Because the surface of the waste residue contains unsaturated thermosetting polyester residues, it is difficult for secondary processing and cannot be degraded in the natural environment, causing serious environmental pollution and becoming the biggest hidden danger behind the bright artificial stone. sustainable development. According to industry introductions, there are more than 200 artificial stone production lines in operation nationwide, and each artificial stone production line produces an average of about 25 tons of calcium carbonate waste every day, which not only causes serious environmental pollution and water pollution, but also a great waste of resources. How to realize the resource utilization and harmlessness of artificial granite solid waste has become the biggest bottleneck to break through the green and sustainable development of the industry.

Polytrimethylene terephthalate (PTT) is a polyester obtained by the polymerization of dimethyl terephthalate or terephthalic acid and 1,3-propanediol. PTT is a promising new polyester polymer newly developed after polyethylene terephthalate (PET) in the 1950s and polybutylene terephthalate (PBT) in the 1970s. Material, in 1998, it was rated as one of the six new petrochemical products by the United States. PTT is a semi-crystalline polymer with high melting temperature and glass transition temperature. It has good wear resistance, heat resistance and chemical resistance. It is widely used in synthetic fibers, films and engineering plastics. . However, the higher price of PTT (mainly due to the higher cost of 1,3-propanediol) and larger molding dimensional shrinkage limit the wider application of PTT.

Although the unsaturated resin coated on the surface of artificial granite waste has structural similarities with PTT, so far, there is no relevant report on the preparation of PTT/artificial granite waste composite material.

[Content of the invention]

One of the objectives of the present invention is to provide a PTT/artificial granite waste residue composite material.

Another object of the present invention is to provide a preparation method of the above-mentioned PTT/artificial granite waste residue composite material.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows:

A PTT/artificial granite waste slag composite material is composed of the following raw materials in parts by weight: 100 parts of dimethyl terephthalate, 5-50 parts of artificial granite waste slag, 80-100 parts of propylene glycol, and 0.01-100 parts of a transesterification catalyst. 0.5 part and polymerization catalyst 0.01-0.5 part.

Further, the artificial granite waste residue is a powdery material with a particle size of less than 30 μm obtained after the waste residue produced in the artificial granite production process is wet granulated, sieved, and dried at 100° C. for 8 hours.

Preferably, the propylene glycol is 1,3-propylene glycol.

Further, the transesterification catalyst is one of antimony trioxide, tetra-n-butyl titanate or K2TiF6.

Further, the polymerization catalyst is one of copper acetate, magnesium acetate or zinc acetate.

The preparation method of the PTT/artificial granite waste residue composite material of the present invention comprises the following steps:

(1) transesterification: dimethyl terephthalate, diol and transesterification catalyst are mixed in proportion to obtain a mixture, then placed in a reactor with stirring, and stirring is started, and the control reaction temperature is 140～205 ℃, Carry out a transesterification reaction;

(2) polymerization: when step (1) generates methanol with a material amount higher than 1.6 times the amount of dimethyl terephthalate material, add a polymerization catalyst, then add artificial granite waste to it, and raise the temperature to 240～280℃, adjust the vacuum degree to below 40Pa to carry out the polycondensation reaction, the reaction time is 4～6h, after the polycondensation is finished, the temperature is controlled to be 60-80℃, and the vacuum drying is performed for 24～48h to obtain the PTT/artificial granite waste residue composite Material.

Further, the reactor is a three-necked flask or a stainless steel reactor.

To sum up, due to the adoption of the above-mentioned technical solutions, the beneficial effects of the present invention are:

Compared with the prior art, the PTT/artificial granite waste slag composite material prepared by the present invention and the preparation method thereof make good use of the special surface characteristics of the artificial granite waste slag and the relatively low viscosity and severe mechanical properties of the in-situ polymerization system. The characteristics of stirring make the artificial granite waste slag disperse evenly in the system, and have good interface compatibility with the PTT matrix, and then the composite material obtained has excellent comprehensive mechanical properties, and heat resistance and molding shrinkage rate are significantly improved.

More importantly, a PTT/artificial granite waste residue composite material prepared by this method is an in-situ polymerization method that does not require any solvent, and is extremely convenient for industrial production.

【Detailed ways】

The present invention will be further described below in conjunction with the embodiments shown. The artificial stone waste residue used was from Guangxi Lisheng Stone Industry Co., Ltd., passed through a 500-mesh sieve (to remove coarser particles) and dried before use.

Example 1:

(1) 100g (0.515mol) dimethyl terephthalate, 80g 1,3-propanediol and 0.01g tetra-n-butyl titanate are added into a 250ml three-necked flask equipped with mechanical stirring, and the controlled reaction temperature is 140°C to carry out transesterification;

(2) After the amount of methanol evaporated by transesterification reaches 33.3ml (0.823mol), 0.01g of zinc acetate and 5g of artificial granite waste residue are added, and the control temperature is 240°C, and the polycondensation reaction is carried out under the pressure of less than 40Pa for 4h, and after the polycondensation is completed The product was obtained by vacuum drying at 80° C. for 24 hours, which was a PTT/artificial granite waste residue composite material. The content of artificial granite waste residue in the composite material is about 4wt%. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

Example 2:

(1) with 100g (0.515mol) dimethyl terephthalate, 85g 1,3-propanediol and 0.05g K TiF Add the 250ml three-necked flask that mechanical stirring is housed, and control temperature of reaction is 160 ℃ to carry out transesterification;

(2) After the amount of methanol evaporated by transesterification reaches 33.3ml (0.823mol), add 0.05g copper acetate, 10g artificial granite waste residue, control the temperature to be 250°C, and perform the polycondensation reaction for 4h under the pressure of less than 40Pa, and after the polycondensation finishes The product was obtained by vacuum drying at 80° C. for 24 hours, which was a PTT/artificial granite waste residue composite material. The content of artificial granite waste residue in the composite material is about 8wt%. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

Example 3:

(1) 100g (0.515mol) of dimethyl terephthalate, 90g of 1,3-propanediol and 0.1g of antimony trioxide were added to a 250ml three-necked flask equipped with mechanical stirring, and the controlled reaction temperature was 180° C. to carry out transesterification ;

(2) After the amount of methanol evaporated by the transesterification reaches 33.3ml (0.823mol), 0.1g of magnesium acetate and 20g of artificial granite waste are added, and the control temperature is 250° C. The polycondensation reaction is carried out under a pressure of less than 40Pa for 4h, and after the polycondensation is completed The product was obtained by vacuum drying at 80° C. for 24 hours, which was a PTT/artificial granite waste residue composite material. The content of artificial granite waste residue in the composite material is about 14wt%. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

Example 4:

(1) 100g (0.515mol) dimethyl terephthalate, 95g 1,3-propanediol and 0.2g tetra-n-butyl titanate are added into the 250ml three-necked flask equipped with mechanical stirring, and the controlled reaction temperature is 205 ° C to carry out transesterification;

(2) After the amount of methanol evaporated by transesterification reaches 33.3ml (0.823mol), 0.3g of zinc acetate and 3g of artificial granite waste residue are added, and the control temperature is 250°C, and the polycondensation reaction is performed for 4h under the pressure of less than 40Pa. After the polycondensation finishes The product was obtained by vacuum drying at 80° C. for 24 hours, which was a PTT/artificial granite waste residue composite material. The content of artificial granite waste residue in the composite material is about 20wt%. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

Example 5:

(1) 100g (0.515mol) dimethyl terephthalate, 100g 1,3-propanediol and 0.5g tetra-n-butyl titanate are added into the 250ml three-necked flask equipped with mechanical stirring, and the controlled reaction temperature is 205 ° C to carry out transesterification;

(2) After the amount of methanol evaporated by transesterification reaches 33.3ml (0.823mol), add 0.5g of zinc acetate, 50g of artificial granite waste residue, control the temperature to be 280°C, and perform a polycondensation reaction for 4h under a pressure of less than 40Pa, and after the polycondensation finishes The product was obtained by vacuum drying at 80° C. for 24 hours, which was a PTT/artificial granite waste residue composite material. The content of artificial granite waste residue in the composite material is about 30wt%. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

In order to better illustrate the important role of the composite of PTT and artificial granite waste residue in the components of the present invention, the comparative example, on the basis of Example 1, investigated the performance influence of the composite material prepared without adding artificial granite waste residue, and the results are shown in the table. 1.

Comparative example:

(1) 100g (0.515mol) dimethyl terephthalate, 80g 1,3-propanediol and 0.01g n-tetrabutyl titanate were added to a 250ml three-necked flask equipped with mechanical stirring, and the control reaction temperature was 200 ° C to carry out ester exchange;

(2) After the amount of methanol evaporated by transesterification reaches 33.3 ml (0.823 mol), add 0.03 g of zinc acetate, control the temperature to be 250°C, perform polycondensation reaction under a pressure of less than 40Pa for 4h, and vacuum dry at 80°C for 24h after the polycondensation is over. The product is obtained, which is pure PTT. The force, thermal properties and molding shrinkage of the samples were measured. The values are shown in Table 1.

Table 1

From Table 1, we found that the addition of artificial granite waste slag greatly improved the thermal stability of PTT and significantly reduced its molding shrinkage while maintaining the high strength of PTT. Therefore, the PTT/artificial granite waste slag composite material has excellent comprehensive properties.

The above description of the embodiments is for the convenience of those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (7)

1. a PTT/artificial granite waste residue composite material, is characterized in that, is made up of the raw material of following parts by weight: 100 parts of dimethyl terephthalate, 5-50 parts of artificial granite waste residues, 80-100 parts of propylene glycol , 0.01-0.5 part of transesterification catalyst and 0.01-0.5 part of polymerization catalyst. 2. PTT/artificial granite waste slag composite material according to claim 1, is characterized in that: described artificial granite waste slag is the waste slag produced in artificial granite production process through wet granulation, sieving, at 100 ℃ The particle size obtained after drying for 8 hours is a powdery material with a particle size of less than 30 μm. 3. The PTT/artificial granite waste residue composite material according to claim 1, wherein the propylene glycol is 1,3-propylene glycol. 4. The PTT/artificial granite waste residue composite material according to claim 1, wherein the transesterification catalyst is one of antimony trioxide, tetra-n-butyl titanate or K ₂ TiF ₆ . 5. PTT/artificial granite waste residue composite material according to claim 1, is characterized in that: described polymerization catalyst is a kind of in copper acetate, magnesium acetate or zinc acetate. 6. the preparation method of the described PTT/artificial granite waste residue composite material of any one of claim 1 to 5, is characterized in that comprising the following steps: (1) transesterification: dimethyl terephthalate, diol and transesterification catalyst are mixed in proportion to obtain a mixture, then placed in a reactor with stirring, and stirring is started, and the control reaction temperature is 140～205 ℃, Carry out a transesterification reaction; (2) polymerization: when step (1) generates methanol with a material amount higher than 1.6 times the amount of dimethyl terephthalate material, add a polymerization catalyst, then add artificial granite waste to it, and raise the temperature to 240～280℃, adjust the vacuum degree to below 40Pa to carry out the polycondensation reaction, the reaction time is 4～6h, after the polycondensation is finished, the temperature is controlled to be 60-80℃, and the vacuum drying is performed for 24～48h to obtain the PTT/artificial granite waste residue composite Material. 7. The preparation method of PTT/artificial granite waste residue composite material according to claim 6, wherein the reactor is a three-necked flask or a stainless steel reactor.