CN103965406A - Melt-grafting modified chlorinated polypropylene and preparation method thereof - Google Patents

Abstract

The invention provides a melt-grafted modified chlorinated polypropylene and a preparation method thereof. The proportions by weight of the melt-grafted modified chlorinated polypropylene include 50-65 parts of chlorinated polypropylene and 20-25 parts of rosin , 10-15 parts of maleic anhydride, 0.1-0.3 parts of initiator. The above-mentioned materials are put into high-speed mixing in proportion, and fed into the ZSK-30 twin-screw extruder. At a feeding speed of 40-50 g/min and a screw speed of 40-60 rpm, through temperature control, the feeding port is 60-80 ℃, melt mixing section 100-120℃, grafting reaction section 175-180℃, extruder head 185℃, and then pull into strips. The product is obtained after cooling and pelletizing. The product prepared from the melt-grafted modified chlorinated polypropylene of the present invention has excellent solubility in some ketone ester solvents, and is suitable for manufacturing environmentally friendly gravure composite inks, paints, coatings, and adhesives without benzols and ketones.

Description

Melt graft modified chlorinated polypropylene and preparation method thereof

technical field

The invention relates to a melt-grafted modified chlorinated polypropylene and a preparation method thereof, in particular to a modified chlorinated polypropylene for producing environmentally friendly gravure composite inks, paints, coatings and adhesives without benzos and ketones and a preparation method thereof.

Background technique

Chlorinated polypropylene (CPP) is a chemically modified product that introduces -Cl groups into polypropylene. It is a white or light yellow solid powder or granular product. It has non-toxic, acid-resistant, water-resistant, good transparency and easy film formation. , not easy to burn and other characteristics, used in coatings, adhesives, ink carriers and leather treatment agents, etc., according to the different degrees of chlorination, chlorinated polypropylene can be divided into high chlorinated polypropylene (chlorination degree 62-67%) ) and low-chlorinated polypropylene (chlorination degree 20-40%) two categories of products. Chlorinated polypropylene (CPP) has achieved considerable development abroad due to its excellent performance and wide application. With the continuous improvement of the demand level of printing, plastic packaging and other industries, coupled with the development of advanced inks, adhesives and coatings, the demand for CPP in the domestic market will increase sharply, especially in the ink industry. The growth rate of demand is the largest. However, due to its molecular structure and molecular polarity, its adhesion, cohesiveness, miscibility and other properties cannot meet the needs of many aspects, and when chlorinated polypropylene is used in inks, paints, coatings and other products, it is difficult to It needs to be dissolved with ketones and benzene solvents, especially "triphenyl" which is flammable, explosive, toxic, harmful to workers' health, and pollutes the environment. Through its chemical modification, while retaining the excellent characteristics of chlorinated polypropylene, the product has significantly improved aging resistance, flame resistance, and corrosion resistance. It is easily soluble in ester solvents and does not need to be dissolved with "triphenyl". Chlorine and other introduced functional groups in chlorinated polypropylene can enhance the active point of chemical reaction and make it have more new functions.

The invention utilizes rosin containing double bonds and carboxyl groups, tertiary hydrogen in chlorinated polypropylene, and double bonds in maleic anhydride to undergo esterification and polymerization reactions for blending and melting graft modification. It is a new type of chlorine with excellent performance. Polypropylene resin.

Contents of the invention

The technical problem to be solved by the present invention is to use rosin containing double bonds and carboxyl groups, tertiary hydrogen in chlorinated polypropylene, and double bonds in maleic anhydride to undergo esterification and polymerization reactions, and carry out blending and melting grafting modification to produce The obtained modified chlorinated polypropylene resin has excellent solubility in some ketone ester solvents, and is suitable for manufacturing environmentally friendly gravure composite inks, paints, coatings, and adhesives without benzols and ketones.

The technical problem to be solved by the present invention is to provide melt-grafted modified chlorinated polypropylene and its preparation method.

The technical scheme that the present invention solves its technical problem is:

1. Melt graft modified chlorinated polypropylene and preparation method thereof, comprising the following steps:

a) At normal temperature, put chlorinated polypropylene, rosin, maleic anhydride, and initiator into a high-speed mixer in proportion, and mix for 10-30 seconds;

b) programmatically heat up each section of the twin-screw extruder to a certain temperature, pass the above-mentioned compound through the feeder of the twin-screw extruder, and add it from the feeding port at a feeding rate of 40 g/min;

c) Through the temperature control of the program, the feeding port is 60-80°C, the melting and mixing section is 100-120°C, the grafting reaction section is 175-180°C, the head is extruded at 185°C, and then drawn into strips, cooled by water, and pelletized That is, get the product.

Wherein the mass ratio of the above-mentioned substances is as follows:

Chlorinated polypropylene 60-65 parts

Rosin 20-25 parts

10-15 parts of maleic anhydride

Initiator 0.1-0.3 parts

The chlorinated polypropylene of the present invention has a molecular weight of 320,000-420,000 and a chlorine content of 30-36%.

The rosin described in the present invention is a super-grade to second-grade quality index of Pinus massoniana or Pinus yunnanensis, with a particle size below 80 mesh.

The initiator described in the present invention is one or more mixtures in azobisisobutyronitrile ABN, azobisisoheptanonitrile, dibenzoyl peroxide BPO, and cyclohexanone peroxide:

Initiator 0.1～0.3

Detailed ways

The present invention will be further described below with specific examples, which are easily grasped and verified by those skilled in the art. The present invention is illustrated by examples, but not limited thereto.

Example 1:

Put 60 parts of chlorinated polypropylene, 25 parts of rosin, 15 parts of maleic anhydride, and 0.1 part of initiator into a high-speed mixer, and mix for 30 seconds. The mixed material is put into the automatic feeder, under the feeding speed of 40 g/min and the screw speed of 40 r/min, the temperature is controlled by the program, the feeding port is 65°C, the melting mixing section is 110°C, and the grafting reaction section is 175°C. The machine head is extruded at 185°C, and then pulled into strips, cooled by water, and pelletized to obtain the product.

Example 2:

Put 65 parts of chlorinated polypropylene, 25 parts of rosin, 10 parts of maleic anhydride, and 0.2 parts of initiator into a high-speed mixer, and mix for 30 seconds. The mixed material is put into the automatic feeder, under the feeding speed of 50 g/min and the screw speed of 60 rpm, the temperature is controlled by the program, the feeding port is 70°C, the melting mixing section is 120°C, and the grafting reaction section is 180°C. The machine head is extruded at 185°C, and then pulled into strips, cooled by water, and pelletized to obtain the product.

The performance index that the modified chlorinated polypropylene resin that embodiment 1-2 makes reaches is as follows:

Table 1 Solubility of modified chlorinated polypropylene resin in different solvents

Note: "√" means complete dissolution, transparent appearance and stable system; "×" means slightly soluble or insoluble

Table 2 Adhesion of modified chlorinated polypropylene resin film on various plastic films

According to the GB/T5210-1985 standard, the test is carried out by the pull-off method.

Claims (5)

1. melt grafting modified chlorinated polypropylene is characterized in that, the parts by weight ratio comprises: Chlorinated polypropylene 60-65 parts Rosin 20-25 parts 10-15 parts of maleic anhydride Initiator 0.1-0.3 parts. 2. The melt-grafted modified chlorinated polypropylene according to claim 1, characterized in that the molecular weight of the chlorinated polypropylene is 320,000-420,000, and the chlorine content is 30-36%. 3. The melt-grafted modified chlorinated polypropylene according to claim 1, characterized in that the rosin is the special grade to secondary quality index of Pinus masson or Yunnan pine, and the particle size is below 80 mesh. 4. The melt-grafting modified chlorinated polypropylene according to claim 1, characterized in that the melt-grafting equipment is a ZSK-30 twin-screw extruder. 5. melting grafting modified chlorinated polypropylene according to claim 1 is characterized in that, rosin, maleic anhydride (MAH) and peroxide initiator are dropped into high-speed mixer in proportion, mix 10-30 Second. The mixed material is put into the automatic feeder, under the feeding speed of 40-50g/min and the screw speed of 40-60r/min, the temperature is controlled by the program, the feeding port is 60-80°C, and the melting and mixing section is 100-120°C , Grafting reaction section 175-180 ℃, extrusion head 185 ℃, and then drawn into strips, cooled by water, pelletized to obtain the product.