阅读说明：本技术 一种双环戊二烯在卫浴材料及其制备方法 (Dicyclopentadiene in bathroom material and preparation method thereof ) 是由 陈旭东 肖作杰 甄智勇 于 2019-09-28 设计创作，主要内容包括：一种双环戊二烯在卫浴材料及其制备方法,包括如下重量份数的组分：双环戊二烯(DCPD)100份,固化剂0.005-0.01份,助溶剂0.05-0.1份,共聚单体0.5-2份,无机填料50-150份,无碱玻纤布50-100份,抗氧剂0.5-1.5份,助抗氧剂0.5-2份,光稳定剂0.1-1份。本发明相对于传统的卫浴材料,具有优良的力学性能,具有高拉伸强度,高抗冲性,优异的耐酸碱性,玻璃化转变温度在140℃以上,固化时间短、所需设备简单,操作简单方便。(A dicyclopentadiene bathroom material and a preparation method thereof comprise the following components in parts by weight: 100 parts of dicyclopentadiene (DCPD), 0.005-0.01 part of curing agent, 0.05-0.1 part of cosolvent, 0.5-2 parts of comonomer, 50-150 parts of inorganic filler, 50-100 parts of alkali-free glass fiber cloth, 0.5-1.5 parts of antioxidant, 0.5-2 parts of antioxidant aid and 0.1-1 part of light stabilizer. Compared with the traditional bathroom material, the material has the advantages of excellent mechanical property, high tensile strength, high impact resistance, excellent acid and alkali resistance, glass transition temperature of more than 140 ℃, short curing time, simple required equipment and simple and convenient operation.)

1. The dicyclopentadiene bathroom material is characterized by comprising the following components in parts by weight: 100 parts of dicyclopentadiene (DCPD), 0.005-0.01 part of curing agent, 0.05-0.1 part of cosolvent, 0.5-2 parts of comonomer, 50-150 parts of inorganic filler, 50-100 parts of alkali-free glass fiber cloth, 0.5-1.5 parts of antioxidant, 0.5-2 parts of antioxidant aid and 0.1-1 part of light stabilizer.

2. The dicyclopentadiene in bathroom material of claim 1, wherein the dicyclopentadiene (DCPD) purity is greater than 90%.

3. The dicyclopentadiene-in-bathroom material of claim 1, wherein the curing agent is a Grubbs first generation ruthenium metal carbene complex catalyst.

4. The dicyclopentadiene bathroom material as in claim 1, wherein the cosolvent is one or a combination of aromatic, ether and alkyl, and is one or a combination of toluene, xylene, diethyl ether and white oil.

5. The dicyclopentadiene bathroom material of claim 1, wherein the comonomer is one or a combination of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).

6. The dicyclopentadiene bathroom material as claimed in claim 1, wherein the inorganic filler is one or more of 300 mesh calcium carbonate, 300 mesh silica powder and 300 mesh aluminum hydroxide.

7. The dicyclopentadiene bathroom material as claimed in claim 1, wherein the alkali-free glass fiber cloth is an alkali-free glass fiber cloth with a thickness of 0.4mm and an areal density of 350g/m²。

8. The dicyclopentadiene bathroom material as in claim 1, wherein the antioxidant is one or more of antioxidant 618, antioxidant 168, antioxidant 1010 and antioxidant 626, and the antioxidant aid is one or more of antioxidant BHP and antioxidant DLTP.

9. The dicyclopentadiene-in-bathroom material of claim 1, wherein the light stabilizer is one or more of UV-9, UV-31, UV-P, UV-326, UV-327, LS-744, LS-770.

10. A method for preparing dicyclopentadiene in a bathroom according to any one of claims 1 to 9, comprising the steps of:

the first step is as follows: uniformly stirring and mixing the monomer, the comonomer, the inorganic filler, the antioxidant aid and the light stabilizer;

the second step is that: mixing a ruthenium carbene catalyst and a cosolvent into a homogeneous solution, preferably mixing the ruthenium carbene catalyst and the cosolvent into a homogeneous solution, and completely dissolving a curing agent in the solution to form a transparent solution;

the third step: mixing the mixed slurry with a catalyst solution at room temperature, and quickly and uniformly stirring;

the fourth step: spreading three layers of glass fiber cloth in a mold;

the fifth step: pouring the mixed slurry obtained in the third step into the mold obtained in the fourth step, and allowing the slurry to completely soak the alkali-free glass fiber cloth and to gel at room temperature;

and a sixth step: and heating and curing the die in the fifth step.

Technical Field

The invention relates to synthesis and application preparation of dicyclopentadiene (DCPD), in particular to dicyclopentadiene in bathroom materials and a preparation method thereof.

Background

The DCPD molecule contains a norbornene ring and a cyclopentene ring, and theoretically, both the norbornene ring and the cyclopentene ring can be opened, but actually, because the ring tension of the norbornene ring is high (the tension of the norbornene ring is 83.6kJ/mol, and the tension of the cyclopentene ring is 20.5 kJ/mol), under a proper catalytic system, the norbornene ring with high tension is easy to generate Ring Opening Metathesis Polymerization (ROMP) to form linear polydicyclopentadiene, and along with the continuous reaction, the double bond of the cyclopentene ring can be partially opened to generate ROMP, so that the PDCPD with a cross-linked structure has high cross-linking degree, a main chain has a large number of ring structures, and a molecular chain has certain rigidity, so the PDCPD has excellent impact strength, high modulus and good thermal stability.

At present, polydicyclopentadiene (PDCPD) is applied more and more in the market, but as a plurality of double bonds exist in a polydicyclopentadiene (PDCPD) macromolecular chain, pi bonds in the double bonds are easy to break under the action of light and oxygen, so that the performance of the material is reduced. The presence of conjugated double bonds is also responsible for yellowing of polydicyclopentadiene. In order to improve the practicability of polydicyclopentadiene, it is necessary to further improve the yellowing resistance and the weather resistance of polydicyclopentadiene.

The bathroom materials adopted in the market at present mainly comprise PVC materials, artificial marble materials and artificial quartz stone materials. Wherein the artificial quartz stone material mainly adopts heavy fillers such as quartz sand and the like. Chinese patent CN103396040B discloses an artificial solid face material and a manufacturing method thereof. Chinese patent CN106243279A discloses a preparation method of polydicyclopentadiene composite material, wherein the problem of ageing resistance of polydicyclopentadiene is solved. However, the yellowing problem of polydicyclopentadiene is not solved, and therefore, further development of a yellowing-resistant and weather-resistant polydicyclopentadiene material is needed. The existing bathroom material has the problems of complex production process, high production cost and the like. The conventional quartz stone and artificial stone are easy to break in the processing process and the like. Therefore, a bathroom material with simple processing technology, low production cost, good toughness, weather resistance and yellowing resistance is needed to be found.

Disclosure of Invention

The invention aims to provide a dicyclopentadiene bathroom material and a preparation method thereof, which have the advantages of excellent mechanical property, high tensile strength, high impact resistance, excellent acid and alkali resistance, glass transition temperature of over 140 ℃, short curing time, simple required equipment and simple and convenient operation, and are used for solving the problems in the background art.

In order to achieve the purpose, the invention provides the following technical scheme: the dicyclopentadiene bathroom material comprises the following components in parts by weight: 100 parts of dicyclopentadiene (DCPD), 0.005-0.01 part of curing agent, 0.05-0.1 part of cosolvent, 0.5-2 parts of comonomer, 50-150 parts of inorganic filler, 50-100 parts of alkali-free glass fiber cloth, 0.5-1.5 parts of antioxidant, 0.5-2 parts of antioxidant aid and 0.1-1 part of light stabilizer.

Further, the dicyclopentadiene (DCPD) preferably has a purity of greater than 90%.

Further, the curing agent is a Grubbs first generation catalyst, which is a ruthenium metal carbene complex catalyst.

Furthermore, the cosolvent is one or a combination of more of aromatics, ethers and alkyls, and most preferably any one or a combination of more of toluene, xylene, diethyl ether, white oil and the like.

Further, the comonomer is one or a combination of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).

Further, the inorganic filler is one or more of 300-mesh calcium carbonate, 300-mesh silicon micropowder and 300-mesh aluminum hydroxide.

Further, the alkali-free glass fiber cloth is alkali-free glass fiber cloth, the thickness of the alkali-free glass fiber cloth is 0.4mm, and the surface density of the alkali-free glass fiber cloth is 350g/m²。

Further, the antioxidant is one or more of antioxidant 618, antioxidant 168, antioxidant 1010 and antioxidant 626, and the auxiliary antioxidant is one or more of antioxidant BHP and antioxidant DLTP.

Further, the light stabilizer is one or more of UV-9, UV-31, UV-P, UV-326, UV-327, LS-744 and LS-770.

The invention also provides a preparation method of dicyclopentadiene in a bathroom, which comprises the following steps:

the first step is as follows: uniformly stirring and mixing the monomer, the comonomer, the inorganic filler, the antioxidant aid and the light stabilizer;

the second step is that: mixing a ruthenium carbene catalyst and a cosolvent into a homogeneous solution, preferably mixing the ruthenium carbene catalyst and the cosolvent into a homogeneous solution, and completely dissolving a curing agent in the solution to form a transparent solution;

the third step: mixing the mixed slurry with a catalyst solution at room temperature, and quickly and uniformly stirring;

the fourth step: spreading three layers of glass fiber cloth in a mold;

the fifth step: pouring the mixed slurry obtained in the third step into the mold obtained in the fourth step, and allowing the slurry to completely soak the alkali-free glass fiber cloth and to gel at room temperature;

and a sixth step: and heating and curing the die in the fifth step.

Compared with the prior art, the invention has the beneficial effects that:

compared with the traditional bathroom material, the high strength, high modulus and high toughness of the polydicyclopentadiene can improve the performance of the bathroom material, the bending strength and bending modulus of the dicyclopentadiene bathroom material are greatly improved by the silica micropowder inorganic filler, the cost is saved, the mechanical property is enhanced, the mechanical property of the polydicyclopentadiene is improved by adding the comonomer MDI, the weather resistance of the polydicyclopentadiene is greatly improved by the synergistic action of the antioxidant 168 and the antioxidant assistant BHP, the yellowing resistance of the polydicyclopentadiene is improved by adding the light stabilizer LS-744, the excellent mechanical property is ensured, the polydicyclopentadiene bathroom material has high tensile strength, high impact resistance and excellent acid and alkali resistance, the glass transition temperature is above 140 ℃, the curing time is short, the required equipment is simple, and the operation is simple and convenient.

Detailed Description

The following examples will explain the present invention in detail, but the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.