阅读说明：本技术 亚磷酸二喹啉酯在pvc钡锌复合热稳定剂中的应用 (Application of biquinoline phosphite ester in PVC barium-zinc composite heat stabilizer ) 是由 刘毓林 廖永林 高尔金 王利锋 陈森方 于 2021-10-22 设计创作，主要内容包括：本发明涉及一种亚磷酸二喹啉酯在PVC钡锌复合热稳定剂中的应用,亚磷酸二喹啉酯其结构式如下：该亚磷酸二喹啉酯化合物以新型的杂环基团代替脂肪族芳香族基团,在制备液体钡锌稳定剂中加入该化合物,可以有效的改善其抗析出性,又具备高效的耐热老化性能(静态稳定性能),在广告膜之类的二次印刷中具有优良的加工性能。(The invention relates to an application of diquinoline phosphite in a PVC barium-zinc composite heat stabilizer, wherein the diquinoline phosphite has the following structural formula:)

1. The application of the biquinoline phosphite ester in the PVC barium-zinc composite heat stabilizer is as follows:

2. the use according to claim 1, for preparing a liquid barium zinc stabilizer, wherein the liquid barium zinc stabilizer is prepared from the following raw materials in parts by weight:

3. the use according to claim 2, wherein the liquid barium zinc stabilizer is processed from the following raw materials in parts by weight;

4. a method of preparing a liquid barium zinc liquid stabilizer according to claim 2 or 3, characterized in that the steps are as follows:

(1) uniformly mixing barium isooctanoate, zinc isooctanoate, barium oleate, zinc oleate, diethylene glycol monobutyl ether and industrial white oil in proportion, and heating to 70-80 ℃ while stirring;

(2) adding the diquinoline phosphite ester in the step (1), heating to 80-90 ℃, adding 2-ethyl acetyl benzoyl methane, and preserving the temperature for 30 +/-5 minutes.

(3) Adding an antioxidant 1010 into the step (2), heating to 105 +/-5 ℃, preserving the temperature for 30 +/-5 minutes, cooling and filtering to obtain the liquid barium-zinc stabilizer.

Technical Field

The invention relates to application of diquinoline phosphite in a PVC barium-zinc composite heat stabilizer.

Background

The traditional barium-zinc PVC composite heat stabilizer has poor compatibility of metal soap and PVC resin, so that the metal soap is continuously separated out in the process of PVC calendering and forming, and the separated out matter is attached to the surface of a PVC film, so that the printing, the painting and the transparency of a product are influenced. Therefore, an anti-precipitation agent needs to be added into the liquid stabilizer, so that the spray painting performance of the PVC film is improved, and precipitation is inhibited. At present, most of the anti-precipitation agents with better use effects in the liquid stabilizer are phenol-containing substances, the dosage of the anti-precipitation agents is 4-10% (accounting for the percentage of the liquid stabilizer), the anti-precipitation agents are applicable to soft PVC films with low environmental protection requirements, but most of toy films exported in Europe and America have strict limitation on phenol (generally below 1000 PPM), so that the development of the anti-precipitation agents without phenol and the application of the anti-precipitation agents in PVC composite heat stabilizers are urgent.

At present, few research reports on the anti-precipitation agent exist, and patent CN201410241381.2 mentions that triphenyl phosphite reacts with water to synthesize diphenyl phosphite, which is an acid phosphite anti-precipitation agent, and the acid phosphite anti-precipitation agent is added into a liquid stabilizer, so that the acid phosphite anti-precipitation agent has a good effect of inhibiting the precipitation of metal soap. However, the compound is extremely easy to decompose in a stabilizer system, generates a large amount of free phenol, and is limited to be applied to export PVC soft products with higher environmental protection requirements.

Patent CN106046618A discloses a bipyridyl phosphite which has the effect of inhibiting the precipitation of metal soap, but has limited aging resistance, so it is limited in its application. The present invention aims to solve this technical problem.

Disclosure of Invention

The invention aims to solve the defects of environmental protection and thermal aging resistance of a precipitating agent in a PVC barium-zinc composite heat stabilizer and provides application of diquinoline phosphite in the PVC barium-zinc composite heat stabilizer. The product is added into a PVC barium zinc composite heat stabilizer product, so that the precipitation of a PVC soft product can be obviously improved, the anti-aging performance of the product can be improved, and the printability of the PVC soft product is improved.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the application of the biquinoline phosphite in the PVC barium-zinc composite heat stabilizer is that the biquinoline phosphite has the following structural formula:

the group replaces aliphatic aromatic group, and the compound is added in the liquid barium zinc stabilizer, so that the precipitation resistance of the barium zinc stabilizer can be effectively improved, and the barium zinc stabilizer has high-efficiency heat aging resistance (static stability) and excellent processing performance in secondary printing such as advertising films.

Preferably, the liquid barium zinc stabilizer is processed from the following raw materials in parts by weight:

preferably, the liquid barium zinc stabilizer is processed from the following raw materials in parts by weight;

preferably, the preparation method of the liquid barium-zinc liquid stabilizer comprises the following steps:

(1) uniformly mixing barium isooctanoate, zinc isooctanoate, barium oleate, zinc oleate, diethylene glycol monobutyl ether and industrial white oil according to a ratio, and heating to 70-80 ℃ while stirring;

(2) adding the diquinoline phosphite ester in the step (1), heating to 80-90 ℃, adding 2-ethyl acetyl benzoyl methane, and preserving the temperature for 30 +/-5 minutes.

(3) Adding an antioxidant 1010 into the step (2), heating to 105 +/-5 ℃, preserving the temperature for 30 +/-5 minutes, cooling and filtering to obtain the liquid barium-zinc stabilizer.

The invention has the beneficial effects that:

(1) the di-quinoline phosphite compound uses a novel heterocyclic group to replace an aromatic group of an aliphatic agent, and shows more excellent precipitation resistance, more excellent coloring property and more excellent aging resistance than aliphatic and aromatic in the application of preparing the liquid barium-zinc stabilizer.

(2) The invention greatly reduces the defect of poor film coloring caused by precipitation. Diethylene glycol butyl ether is added into the system to improve the compatibility among all components in the system, thereby achieving the uniformity of the product. The good stability of the product in the initial stage and the later stage is ensured, the precipitation performance of the product is improved, the printing performance of the PVC product is improved, and the market competitiveness of the product is improved.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples.

The raw materials used in the examples are all conventional raw materials on the market.

Preparation of a bisquinoline phosphite:

using 68.7g of phosphorus trichloride and 228.4g of 8-hydroxyquinoline as raw materials, dropwise adding phosphorus trichloride into 8-hydroxyquinoline at the temperature of 70 ℃ for 120 minutes to obtain trioline phosphite; 20.5g of phosphorous acid was charged into the above product, and the reaction was carried out at 120 ℃ for 60 minutes to obtain 168g of diquinoline phosphite.

The formulations of the liquid barium zinc stabilizers of examples 1-4 are as follows:

the preparation of the liquid barium zinc stabilizers of examples 1-4 was carried out according to the following procedure:

(1) adding barium isooctanoate, zinc isooctanoate, barium oleate, zinc oleate, diethylene glycol monobutyl ether and industrial white oil into a reactor according to a proportion, and heating to 70-80 ℃ while stirring;

(2) adding 2-ethyl acetyl benzoyl methane into the step (1), heating to 85-90 ℃, and preserving heat for 30 minutes; then adding the diquinoline phosphite, and stirring for 30 minutes at the temperature of 85-90 ℃;

(3) adding an antioxidant 1010 into the step (2), heating to 105 ℃, preserving the heat for 30 minutes, cooling and filtering to obtain the liquid barium-zinc stabilizer.

First, heat aging stability test

(1) The soft PVC formula comprises:

verification examples 1 to 4: PVC (SG-1000, Qilu, China petrochemical Co., Ltd.); 100g, liquid stabiliser prepared for experiments 1-4: 3g, DOP (Chinese petrochemical, Qilu Ltd.): 35g of

(2) Preparation of a sample:

according to the soft PVC formulation, the materials were mixed well and refined on an open mill (Shanghai Hongyang group) at 179 + -2 deg.C for about 3 minutes to prepare PVC test pieces with a thickness of about 1 mm.

Testing the thermal stability of the PVC test piece according to the following method;

the prepared PVC test piece is cut into a sheet sample, and the temperature of a 401A aging test box (Shanghai brocade instrument and meter factory) is set to be 185 +/-2 ℃ in the experiment. When the thermostatic lamp of the 401A aging box is on, 6-8 chips are quickly hung (the direction is vertical to the turntable) to be uniformly distributed in space. Rotating and blowing. Taking out a piece of sample every 10min, wherein the temperature after each sampling is not lower than 175 ℃, and cooling the test piece. Cut into 30mm × 12mm and attached to the original report sheet. The time when the test piece begins to turn black is the thermal aging time. The results are as follows:

verification example	Static thermal stability time, min
		Verification example 1	55
Verification example 2	62
		Verification example 3	68
Verification example 4	75

II, a precipitation experiment formula:

(1) basic formula

Verification examples 1 to 4: PVC (SG-1000, Qilu, China petrochemical Co., Ltd.): 100g, Experil.1-4 barium Zinc stabilizer: 4g, DOP (Chinese petrochemical, Qilu Ltd.): 35g of red pigment: 1g

(2) The formula of the white material comprises:

PVC (SG-1000, Qilu, China petrochemical Co., Ltd.): 100g of methyl tin composite heat stabilizer (Zhejiang Haiputon New materials Co., Ltd.): 1g, DOP (Chinese petrochemical, Qilu Ltd.): 35g, stearic acid (hangzhou oil): 1g of titanium dioxide (DuPont corporation): 7g

(3) Sample preparation:

according to the above soft product formula, accurately weighing the materials respectively, mixing well, refining at 180 + -2 deg.C on an open type rubber refining machine (Shanghai Hongyang group) according to the basic formula for 8 minutes, taking down the refined red material, adding the white material onto an unwashed double roller, refining for 5 minutes, taking down the refined material, making into PVC sample sheet with thickness of about 1mm, detecting Da value, observing precipitation, the results are as follows:

examples	Verification example 1	Verification example 2	Verification example 3	Verification example 4
					Da value	1.2	0.5	0.1	0

The static thermal stability and precipitation results show that: the liquid barium-zinc stabilizer containing the diquinoline phosphite ester is used for processing PVC products and has excellent precipitation resistance and thermal aging resistance.

The above-described embodiment is only one embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.