CN112321893B

CN112321893B - Plasticizer gel for PVC

Info

Publication number: CN112321893B
Application number: CN201910715188.0A
Authority: CN
Inventors: 万同; 李雪晶; 王曼; 王劭妤; 单鸣达
Original assignee: Tianjin University of Science and Technology
Current assignee: Tianjin University of Science and Technology
Priority date: 2019-08-05
Filing date: 2019-08-05
Publication date: 2022-11-08
Anticipated expiration: 2039-08-05
Also published as: CN112321893A

Abstract

The invention designs the structure and the synthesis formula of the polyurethane gel factor. The gelator is utilized to form organic gel in phthalate plasticizer, and the phthalate organic gel is utilized to prepare the formula of soft PVC. The invention provides a method for adding the gelator into the plasticizer, so that the gelator forms a rod-shaped, fibrous or sheet-shaped reinforced structure through self-assembly, and the plasticizer is gelatinized at the same time, thereby achieving the purpose of enhancing the mechanical property of PVC without greatly reducing the toughness. The invention relates to the fields of polymer material preparation technology and composite material processing technology, in particular to a method for synthesizing a polyurethane organogel factor and reinforcing soft PVC by using organogel of the polyurethane organogel factor.

Description

Plasticizer gel for PVC

Technical Field

The invention relates to the fields of polymer material preparation technology and composite material processing technology, in particular to a polyurethane organogelator and a plasticizer gel formed by the polyurethane organogelator to enhance the mechanical property of PVC.

Background

In recent years, organic gels have attracted attention because of their important application values in cosmetics, chemical separations, drug delivery, and smart materials. The organic oil gel is formed by gelling oil substances by using a gelator to form a semi-solid viscoelastic body. These oil gels are mainly formed by self-assembly of a rodlike, fibrous, sheet-like or other network structure in oil through hydrogen bonding interaction, pi-pi stacking, van der waals force and the like among molecules of a gelator, and the oil is wrapped to gel oil molecules. The invention utilizes the characteristic of self-assembly of the gelator in the plasticizer to gelatinize the plasticizer and applies the gelator to the PVC material so as to improve the performance of the PVC material.

Problems to be solved by the invention

One of the traditional methods for improving the PVC performance is to directly add solid nano-particles and a plasticizer into PVC as an additive to achieve the purpose of reinforcement, but the problems of poor dispersibility of the added nano-particles in PVC, great reduction of toughness and the like are not solved well. The invention provides a method for enhancing the mechanical property of PVC by adding a gelator into a plasticizer, so that the gelator is self-assembled into a network enhanced structure and the plasticizer is gelatinized, and the aim of enhancing the mechanical property of PVC is achieved by utilizing the self-assembled structure without greatly reducing the toughness.

Disclosure of Invention

In view of the above problems, the present invention provides a simple method for preparing a polyurethane gelator and an organogel.

The technical scheme of the invention is as follows:

1. the structural formula of the amino ester organogelator is as follows:

wherein, X is:

y is:

CnH2n + 1-where n is 4-18. The synthesis of the polyurethane gel factor uses raw materials of a compound containing an isocyanate group and fatty alkyl monohydric alcohol respectively; wherein the compound containing isocyanate groups comprises: diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), fatty alkyl monohydric alcohol raw material comprises: c _n H _2n+1 -OH, wherein the number of C is any number from 4 to 18. Mixing fatty alkyl monohydric alcohol, a compound containing isocyanate group and ethyl acetate according to a certain proportion. The mass fractions of the components are respectively 10-70% of fatty alkyl alcohol, 10-55% of compound containing isocyanate group and 10-25% of ethyl acetate, and the reaction is carried out for 4-5 hours under the conditions of 90-110 ℃ and nitrogen protection. And decompressing the product obtained by the reaction by using a rotary evaporator to remove ethyl acetate, and drying the product in a vacuum drying oven to obtain the gel factor of the polyurethane.

2. Phthalate ester oil plasticizer organogel with polyurethane gel factor. Mixing the phthalate ester oil plasticizer and the polyurethane gel factor according to a certain proportion. The mass fractions of the components are respectively 80-98% of phthalate ester oil plasticizer and 1-5% of polyurethane gel factor; heating to 120-240 ℃ to ensure that the polyurethane gel factor is completely melted, and then cooling to room temperature to obtain the phthalate oil plasticizer gel.

3. Phthalates are a class of plastics plasticizers. Refers to esters of phthalic acid with alcohols having from 4 to 15 carbon atoms. Also included are organic solvents used which are diisooctyl phthalate (DOP), diisononyl phthalate, di-n-butyl phthalate, diisodecyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, di-n-octyl phthalate, dimethyl phthalate, dipentyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dipropyl phthalate, dinonyl phthalate, dipropyl phthalate, di-2-methoxyethyl phthalate, didecyl phthalate, di-n-hexyl phthalate, diphenyl phthalate, diphenylmethyl phthalate.

4. The formula for preparing soft PVC by using phthalate ester oil plasticizer organogel. Mixing the phthalate ester oil plasticizer organogel, the PVC resin SG-5 type grease and the Ca-Zn composite stabilizer according to a certain proportion. The mass fractions of the components are respectively 30-60% of phthalate ester oil plasticizer, 40-60% of PVC resin SG-5 type and 1-10% of Ca-Zn composite stabilizer. Pre-heating and mixing by a high-speed mixer, and extruding by a conical co-rotating double-screw extruder.

The beneficial effects of the invention are:

the invention has the innovation that the polyurethane gel factor is self-assembled into a rod-shaped, fibrous or flaky network structure in the plasticizer, and the modulus and the strength of PVC can be enhanced by using the gel in the PVC, so that the toughness is not greatly reduced.

Detailed Description

Example 1:

27g of lauryl alcohol and 12g of ethyl acetate are weighed and added into a three-neck flask, and the mixture is heated, stirred and dissolved. MDI with the mass of 12.5g and 20g of ethyl acetate are weighed into a beaker to dissolve the MDI, and then the dissolved MDI solution is added into a three-neck flask through a separating funnel. The reaction was maintained at 70 ℃ for 5 hours. And (3) evaporating the product obtained by the reaction under reduced pressure by using a rotary evaporator to remove the residual ethyl acetate, and drying the product in a vacuum drying oven to obtain the polyurethane gel factor.

The steps for preparing the plasticizer gel by utilizing the polyurethane gelator are as follows: mixing diisooctyl phthalate (DOP) plasticizer and polyurethane gelator. Continuously heating (the temperature is not more than 180 ℃ at most) until the polyurethane gel factor is completely melted, then keeping the temperature for about three minutes, and then cooling to room temperature to obtain the DOP plasticizer gel.

PVC was prepared using the DOP plasticizer gel described above. 100 parts of PVC, 50 parts of DOP plasticizer gel and 5 parts of Ca-Zn composite stabilizer are weighed, mixed at a high speed and extruded by a conical co-rotating double-screw extruder. PVC/DOP plasticizer gel specimens were prepared in a 170 ℃ dumbbell-shaped mold using a tablet press. The control experiment with DOP without added polyurethane gelator was as follows: 100 parts of PVC, 50 parts of DOP plasticizer gel and 5 parts of Ca-Zn composite stabilizer are weighed and subjected to the same experiment process. PVC/DOP bars were prepared.

Results of Performance testing

The stretching is carried out on a CMT4503 type microcomputer control electronic universal testing machine, and the stretching speed is 10mm/min. The PVC/DOP plasticizer gel specimen had a tensile modulus of 10.6MPa and an elongation at break of 440.4%. The tensile modulus of the PVC/DOP/gel strip was 17.4MPa and the elongation at break was 431.7%. The tensile modulus of the PVC product added with DOP gel is improved by 64.1 percent, and the tensile strength is improved by 19.8 percent.

Claims

1. A method for preparing phthalate ester oil plasticizer organogel containing polyurethane organogel factors is characterized in that: mixing phthalate ester oil plasticizer and polyurethane organogelator in a certain proportion; the mass fractions of the components are respectively 80-98% of phthalate ester oil plasticizer and 1-5% of polyurethane organogel factor; heating to 120-240 ℃ to ensure that the polyurethane organogel factor is completely melted; then cooling to room temperature to obtain phthalate ester oil plasticizer gel;

the structural formula of the polyurethane organogelator is as follows:

wherein, X is:

y is:

C _n H _2n+1 -wherein n is 4-18.

2. The method of claim 1, wherein: the phthalate ester oil plasticizer is an ester of phthalic acid and an alcohol having 4 to 15 carbon atoms.

3. The method of claim 2, wherein: the phthalate-based oil plasticizer further includes diisooctyl phthalate, diisononyl phthalate, di-n-butyl phthalate, diisodecyl phthalate, diisobutyl phthalate, butylbenzyl phthalate, di-n-octyl phthalate, dimethyl phthalate, dipentyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dipropyl phthalate, dinonyl phthalate, di-2-methoxyethyl phthalate, didecyl phthalate, di-n-hexyl phthalate, diphenyl phthalate, diphenylmethyl phthalate.

4. A process for the preparation of flexible PVC using the phthalate ester oil plasticizer organogel prepared by the process of claim 1, characterized in that:

the organic gel of the phthalate ester oil plasticizer, the PVC resin SG-5 type grease and the Ca-Zn composite stabilizer are mixed according to a certain proportion, the mass fractions of the organic gel, the PVC resin SG-5 type grease and the Ca-Zn composite stabilizer are respectively 30-60% of the phthalate ester oil plasticizer, 40-60% of the PVC resin SG-5 type grease and 1-20% of the Ca-Zn composite stabilizer, the sum of the mass fractions of the components is 100%, the components are preheated and mixed by a high-speed mixer and extruded by a conical co-rotating double-screw extruder.