CN112029205A

CN112029205A - Environment-friendly composite plastic with pearlescent effect and multicolor pattern effect and preparation method thereof

Info

Publication number: CN112029205A
Application number: CN202010913595.5A
Authority: CN
Inventors: 刘思妮; 刘青
Original assignee: Nanjing Yuanchu Technology Co ltd
Current assignee: Nanjing Yuanchu Technology Co ltd
Priority date: 2020-09-03
Filing date: 2020-09-03
Publication date: 2020-12-04
Anticipated expiration: 2040-09-03
Also published as: CN112029205B

Abstract

The invention belongs to the technical field of plastic preparation, and relates to environment-friendly composite plastic with pearlescent effect and multicolor pattern effect and a preparation method thereof; the plastic consists of 70-200 parts of styrene thermoplastic resin, 40-100 parts of auxiliary material, 1-20 parts of macromolecular compatilizer, 0.1-10 parts of auxiliary agent, 0.1-5 parts of lubricant and 0.1-4 parts of color master batch; the auxiliary materials are MS, HIPS and PP; the auxiliary agent consists of an anti-aging agent, ultraviolet resistance and inorganic or organic fillers; the invention can improve the appearance of the plastic without adding pearl powder, pearl color master batch or special color master batch, and has pearl effect and multicolor pattern effect; the process is simple, safe and environment-friendly, and avoids the high cost and pollution of secondary processing of plastic products; meanwhile, the invention can adjust the mechanical physical property and the processing property to meet various practical application scenes, make up the defects of the existing plastic products, has high yield and low cost, and is suitable for large-scale production.

Description

Environment-friendly composite plastic with pearlescent effect and multicolor pattern effect and preparation method thereof

Technical Field

The invention belongs to the technical field of plastic preparation, and particularly relates to environment-friendly composite plastic with a pearlescent effect and a multicolor pattern effect and a preparation method thereof.

Background

Plastics are increasingly used because of their excellent properties that many other materials do not have; the plastic product is not only widely applied to industries such as automobiles, household appliances, buildings and the like, but also increasingly adopted in industries such as daily life living, traveling, learning, entertainment and the like of people. With the promotion of novel urbanization construction, adjustment of economic structure and industrial upgrading of China, the quantity of national consumers in China is enlarged, the consumption level is improved, and the contradiction between consumer products and environmental pollution is more and more serious. Nowadays, people have higher requirements on the performance and appearance of plastic products, and also have higher requirements on the environmental pollution and sustainability of the plastic products.

The pearly luster is always pursued by people from ancient times to present due to the magnificent color and elegant quality, is applied to a plurality of industries such as automobiles, household appliances, home furnishing, packaging and the like, and the pattern effect is also favored by people due to the natural and random agility, so the pattern effect is also applied to various fields in the life of people. In order to meet the aesthetic requirements of people, plastic products on the market at present usually adopt various processes such as spraying, printing, pasting, film covering and the like to increase the pearlescent effect and the multi-color pattern effect of the products, or add pearlescent powder, pearlescent color master batch or special color master batch in the injection molding process to enable the plastic products to have the pearlescent effect or the multi-color pattern effect. Although the process meets the visual requirements of people, a large amount of waste water, waste materials, flammable and explosive chemical solvents and the like are generated in the production process, so that the process causes serious harm to the environment, and has the disadvantages of troublesome processing procedure, low yield, high cost and difficult recovery.

Therefore, a method is needed to be researched, so that the plastic product can have a pearly luster effect or a multicolor pattern effect without adding pearl powder, pearl color master batch or special color master batch and the like, and the pollution problem and the recovery problem caused by secondary processing of the plastic product are solved; on the other hand, no report exists at present on an environment-friendly composite plastic with a pearlescent effect and a multicolor pattern effect and a preparation method thereof.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to overcome the technical defects in the prior art and provide the environment-friendly composite plastic with the pearl effect and the multicolor pattern effect and the preparation method thereof. The raw materials related by the invention are easy to obtain in the market, the cost is reasonable, the yield is high, the production process and the final product have no three wastes, and the method is safe and environment-friendly; and the process has good compatibility with equipment, and is suitable for large-scale mass production.

The present invention achieves the above-described object by the following technical means.

The invention firstly provides an environment-friendly composite plastic with pearlescent effect and multicolor pattern effect, which comprises the following components in parts by weight: 70-200 parts of main material, 40-100 parts of auxiliary material, 1-20 parts of high-molecular compatilizer, 0.1-10 parts of auxiliary agent, 0.1-5 parts of lubricant and 0.1-4 parts of color master batch;

the main material is styrene thermoplastic resin;

the main material is a novel micro-phase separation material, and is a multi-block high molecular copolymer formed by connecting plastic molecular aggregates and rubber molecular aggregates by covalent bonds; therefore, the rubber has the characteristics of easy processing of plastics and high elasticity of rubber, and is greatly different from common plastics and rubber.

Preferably, the main material is styrene-butadiene transparent impact-resistant resin.

The auxiliary materials are any one or more of styrene-methyl methacrylate copolymer (MS), polypropylene (PP), polyethylene oxide (PEO), Polyethylene (PE), Polybutylene (PB), Polyisobutylene (PIB), High Impact Polystyrene (HIPS), ethylene propylene rubber and styrene thermoplastic elastomer (SBS, SIS or SEBS);

preferably, the auxiliary materials are styrene-methyl methacrylate copolymer (MS), High Impact Polystyrene (HIPS) and polypropylene (PP).

The high molecular compatilizer is any one or more of polyolefin and maleic anhydride graft copolymer (PP-G-MAH), ethylene-octene copolymer (POE), styrene and acrylonitrile copolymer (SAN) and maleic anhydride graft acrylonitrile-butadiene-styrene copolymer (ABS-G-MAH);

preferably, the high molecular compatilizer is a polyolefin and maleic anhydride graft copolymer (PP-G-MAH), an ethylene-octene copolymer (POE) and/or a styrene and acrylonitrile copolymer (SAN).

The auxiliary agent consists of an anti-aging agent, ultraviolet resistance and inorganic or organic filler; the specific type of the anti-aging agent is any one or more of 1010, 168 or 1076; the specific type of the ultraviolet resistant agent is one or more of UV-531 and UV-376, and the inorganic or organic filler is titanium dioxide (TiO)₂) Or stearic acid (Hst).

Preferably, the auxiliaries are 1076, 168, UV-531 and stearic acid (Hst).

The lubricant is one or more of calcium stearate (Cast), Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS) paraffin, polyethylene glycol (PEG) or random polypropylene;

preferably, the lubricant is calcium stearate (Cast), Ethylene Bis Stearamide (EBS) and pentaerythritol stearate (PETS).

The color master batch is an organic color master batch taking PP and PS as carriers and a pigment as an auxiliary material; the pigment is phthalocyanine blue, phthalocyanine green, fluorescent yellow YG-51 or permanent red F₅Any one of ROr a plurality thereof;

the invention also provides a preparation method of the environment-friendly composite plastic with the pearl effect and the multicolor pattern effect, and the preparation method of the composite plastic comprises the following steps: the initial material mixing uses a 50-liter sealed high-speed stirrer, the rotating speed of the stirrer is less than or equal to 3000rpm, the regulation is convenient, the material temperature is indicated to record the mixing temperature, and the material temperature is controlled by the rotating speed and the mixing time. So that the initial-mixing final temperature can be controlled within the range of 40-80 deg.C.

The method comprises the following specific steps:

(1) according to the weight parts, firstly, taking the main material, the auxiliary material and the high-molecular compatilizer, stirring at a low speed to uniformly mix the materials until the materials are not adhered to a sheet, a wall or a sediment; the optimal initial mixing condition is corresponding to a composite plastic system and is determined by self test and investigation;

(2) stopping the high-speed mixer, adding the uniformly mixed auxiliary agent and lubricant after the cover opening inspection meets the requirements (the materials are not adhered to the pieces and are not adhered to the wall or deposited on the bottom), covering the cover, timing, adjusting the rotating speed, starting stirring, stirring for a certain time, observing the temperature to 40-80 ℃, stopping the cover opening inspection, and uniformly adhering the powder to the surface of the granular material when the powder is not deposited on the bottom or adhered to the wall to meet the requirements to obtain the material of a primary mixing grid;

(3) placing the materials in the primary mixing grid into an enamel tray or a stainless steel tray, and spreading and paving for later use;

(4) setting the screw rotating speed of a unit and the temperature of a granulator of a twin-screw devolatilization extrusion granulator set, feeding the materials spread and spread in a primary mixing grid into a homodromous twin-screw mixing granulator in a streamline form from top to bottom cutting mode for melting mixing and extrusion granulation, and feeding the materials along the edge when the materials are added into the extrusion granulator; the double-screw unit is divided into 12 sections of independent temperature control areas, and a normal pressure exhaust port and two vacuum exhaust ports are respectively arranged at 6 sections, 8 sections and 10 sections to ensure that low boiling point substances are vacuum-extracted and volatile matters are reduced to be below 0.2%; the molten material strip extruded from the die head of the extruder enters a cooling water tank and a granulator to finally obtain environment-friendly composite plastic granules with the diameter of 3x5mm and the effects of pearlescence and multicolor patterns;

(5) and adding the environment-friendly composite plastic granules and the color master batch into an injection molding machine according to corresponding use amounts for injection molding, wherein the injection molding temperature is 160-220 ℃, the maximum volume of a control mold is 60-70% of the injection molding amount of the machine, the injection pressure is 3 PMA-8 PMA, the pressure maintaining time is 10-20 seconds, the fullness degree of the inner cavity of the mold is ensured, and after the materials are cooled and molded, demolding is carried out, so that an injection molding finished product, namely the environment-friendly composite plastic product with the pearlescent effect and the pattern effect is obtained.

Further, in the step (1), the rotation speed of stirring is 1000-3500 rpm, and the time is 1-10 min.

Further, in the step (2), the rotating speed of the continuous stirring is 1000-3500 rpm, and the stirring is carried out for 1-10 min.

Further, in the step (4), the rotating speed of the group of screws is 100-500 rpm; the temperature of the granulator is as follows: the temperature is 150-210 ℃, and the specific temperature rising program is as follows: the temperature of the material is gradually increased from the inlet to 190-210 ℃ from 150 ℃, and then is reduced to 180-200 ℃ of the die.

In addition, after the mixing conditions of the two sections of initial mixing corresponding to one composite plastic formula are determined, the operation can be rapidly, stably and repeatedly carried out in the continuous large-scale production.

The composite plastic is melted, mixed, extruded and granulated by adopting a double-screw devolatilization extrusion granulator set; the used extrusion granulator set is a special device designed by the company, and the devolatilization extruder has the screw diameter of 25 and the L/D of 48; the quality of the machine set product mainly depends on the type, the geometric dimension and the arrangement sequence of the thread elements. Considering the characteristic that materials such as PP and the like are easy to degrade, the extrusion granulator reduces the shearing degree of materials on the aspect of screw element composition, improves the surface renewal speed by deformation to improve the mixing effect, can adjust the rotation speed of a screw of a unit at 100-500 rpm, and can adjust and control according to the different formulas and capacities of master batches. The twin-screw unit is divided into 12 sections of independent temperature control areas, and a water cooling and heating system is automatically adjusted according to a set value. A single-screw feeder and a charging hopper are arranged on the feeding port; the rotating speed of the feeding machine is adjustable, the feeding speed is matched with that of a main machine screw rod, and the screw rod material is kept at 60-70% of full degree.

The temperature of the material is gradually increased from an inlet, generally from 150 ℃ to 190-210 ℃, and then is reduced to 180-200 ℃ of a probe so as to ensure the aim of full melting and mixing, and the heating temperature of the mixture is controlled as low as possible. Three exhaust ports on the unit are used for exhausting air carried by solid materials and original organic volatile substances of various raw materials, and finally the exhaust ports can be vacuumized to reduce the volatile substances to be below 0.2%. And (3) enabling the molten material strips extruded from the die head of the extruder to enter a cooling water tank and a granulator, and adjusting the rotating speed of the granulator to enable the feeding speed to be matched with the rotating speeds of the extruder and the cutter.

The invention has the advantages and technical effects that:

(1) according to the invention, when the pearl effect and the multicolor pattern effect are obtained by matching the main material with the common color master batch, the physical property parameters of the final finished product can be controlled in a large range by adjusting the specific formula proportion of the main material; the invention can improve the appearance of the plastic without adding pearl powder, pearl color master batch or special color master batch, so that the plastic has both pearl effect and multicolor pattern effect, the rate of finished products is improved, and the cost is reduced. Simultaneously, the pollution problem and the recovery problem caused by secondary processing of plastic products are solved; at present, how to obtain specific multicolor pattern effect and how to simultaneously use specific raw materials to obtain specific physical properties is not the basic common knowledge in the industry, wherein the content relates to three parts of a formula, a mixed granulation process and injection molding equipment selection and process, and based on the three parts, the environment-friendly composite plastic with the pearlescent effect and the pattern effect is obtained; the invention has good effect and obvious progress.

(2) The composite plastic prepared by the invention is safe and environment-friendly, simultaneously meets the requirement of modern plastic products on attractive appearance, and can greatly adjust the mechanical physical property and the processing property so as to meet the fields of various practical application scenes, such as high-grade cosmetic bottle containers, medicine and food packages, toys, electronic products, artware, stationery, medical appliances, instruments and meters and the like.

Drawings

FIG. 1 is a picture of the appearance of an environmentally friendly plastic prepared in example 3 of the present invention.

Detailed Description

The invention is further illustrated by the following examples.

Example 1:

(1) firstly, accurately weighing the main material, the auxiliary material and the high-molecular compatilizer according to the parts shown in the table 1, and then adding the main material, the auxiliary material and the high-molecular compatilizer into a high-speed stirrer, wherein the specific reagents are selected from butylbenzene transparent impact-resistant resin 803, PP, SAN, POE, MS, PP-G-MMA and HIPS; performing primary mixing for 3 minutes at 2000 r/min to make the added substances uniformly mixed, but not stick to pieces, wall and bottom;

(2) stopping the high-speed mixer, after the cover opening inspection meets the requirement of the complaint, adding an auxiliary agent and a lubricant, selecting EBS, PETS, an antioxidant 168, an antioxidant 1010, Cast, Hst and a light stabilizer UV-531 as specific reagents, uniformly mixing the reagents to obtain powder, covering the mixer, continuously stirring the mixture, and performing primary mixing for 5 minutes under the condition of 2000 revolutions per minute to ensure that the powder is adsorbed on plastic particles, wherein the final temperature of the primary mixing is 65 ℃, stopping the cover opening inspection to obtain a material of a primary mixing grid, wherein the powder does not sink or stick to the wall, and is uniformly adhered to the surface of the granules;

(3) placing the materials in the primary mixing grid into an empty tray or a stainless steel tray, spreading and spreading, putting into a co-rotating twin-screw mixing granulator for fine mixing granulation, feeding along the edge when adding into a twin-screw extrusion granulator, and adding in a cutting mode from top to bottom in a streamline manner; the conveying capacity of a single-screw feeder and an extrusion granulator is 1-2 kg/h, the screw rotating speed of the unit is 200rmp, and the temperature of the granulator is arranged as follows: 150 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 200 deg.C, 190 deg.C, 180 deg.C; the 6 section, the 8 section and the 10 section are respectively provided with a normal pressure exhaust port and two vacuum exhaust ports to ensure that low boiling point substances are pumped out in vacuum. The molten material strip extruded from the die head of the extruder enters a cold water tank and a granulator to finally obtain environment-friendly gulhe plastic granules with the diameter of 3x5mm and the pearl effect and the pattern effect;

(4) adding the granules prepared in the step (3) and color master batch into an injection molding machine for injection molding; the injection molding temperature is 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃, the maximum volume of the control mold is 70 percent of the injection molding amount of the machine, the injection pressure is 3 PMA-8 PMA, the pressure maintaining time is 10-20 seconds, and the fullness degree of the inner cavity of the mold is ensured; and cooling and molding the materials, and demolding to obtain the injection molding finished product with the pearl effect and the pattern effect.

Table 1: the components and weight proportions of example 1 are as follows:

example 2:

the components and ratios of example 2 are shown in the table below, and the specific preparation process is the same as example 1.

Table 2: composition and weight ratio of example 2

Example 3:

the components and ratios of example 3 are shown in the table below, and the specific preparation process is the same as example 1.

Table 3: composition and parts by weight of example 3

Example 4:

the components and ratios of example 4 are shown in the table below, and the specific preparation process is the same as example 1.

Table 4: composition and parts by weight of example 4

Comparative example:

the ingredients were weighed accurately according to the ratios in table 1 and then added to a high speed mixer for premixing. And (3) carrying out melt blending and extrusion on the mixture by using a double-screw extruder, feeding the extruded material strip into a water-cooled granulator for granulation, and obtaining the granular plastic alloy by using the same specific processing technology as that of the example 1. And adding the granular plastic alloy and the color master batch into an injection molding machine according to a ratio, and performing injection molding to obtain a plastic product.

Table 1: components and proportions of comparative examples

Table 5: comparative table of properties of various examples

Item	Comparative examples	Example 1	Example 2	Example 3	Example 4
						Yield strength (Mpa)	27.2	26.1	26.5	28.0	29.0
Elongation at yield (%)	0.9	0.9	0.8	0.9	1.0
						Breaking stress (Mpa)	33.0	30.7	31.0	34.2	35.0
Elongation at Break (%)	80.5	74.9	72.4	89.0	98.3
						Maximum bending strain (%)	1.3	1.4	1.4	1.5	1.5
Flexural modulus (Mpa)	1150	1100	1100	1120	1200
						Flexural strength (Mpa)	14.0	13.6	13.5	13.8	14.3
Cantilever impact strength (KJ/square meter)	6.00	6.02	7.5	7.65	8.7
						Vicat softening point (. degree. C.)	90.5	84.2	85.1	86.4	90.5
Hardness (Shao D)	73	70.0	69.0	70.0	72.1
						Melt index (200 ℃, 5kg)	6.5	7.8	8.5	7.24	9.2
Workability	Superior food	Superior food	Superior food	Superior food	Superior food
						Colorability of organic pigments	Superior food	Superior food	Superior food	Superior food	Superior food
Pearlescent effect/pattern	None/none	Weak/shao	In/in	High/much	High/much

According to the data, the pearl effect and the pattern effect of the plastic are obviously improved by adjusting the formula data on the premise of not influencing the physical properties of the plastic; the preparation method has high yield, no three wastes in the production process and the final product, safety and environmental protection; and the process has good compatibility with equipment, and is suitable for large-scale mass production.

The names of the corresponding specific components are as follows:

description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.

Claims

1. The environment-friendly composite plastic with the pearlescent effect and the multicolor pattern effect is characterized by comprising the following components in parts by weight: 70-200 parts of main material, 40-100 parts of auxiliary material, 1-20 parts of high-molecular compatilizer, 0.1-10 parts of auxiliary agent, 0.1-5 parts of lubricant and 0.1-4 parts of color master batch;

the main material is styrene thermoplastic resin;

the auxiliary material is any one or more of styrene-methyl methacrylate copolymer, polypropylene, polyethylene oxide, polyethylene, polybutylene, polyisobutylene, high impact polystyrene, ethylene propylene rubber and styrene thermoplastic elastomer;

the macromolecular compatilizer is any one or more of polyolefin and maleic anhydride graft copolymer, ethylene-octene copolymer, styrene and acrylonitrile copolymer and maleic anhydride graft acrylonitrile-butadiene-styrene copolymer;

the auxiliary agent consists of an anti-aging agent, ultraviolet resistance and inorganic or organic filler; the anti-aging agent is any one or more of 1010, 168 or 1076; the anti-ultraviolet agent is UV-531 or UV-376; the inorganic or organic filler is titanium dioxide or stearic acid.

The lubricant is one or more of calcium stearate, ethylene bis-stearic acid amide, pentaerythritol stearate paraffin, polyethylene glycol or random polypropylene;

the color master batch is an organic color master batch taking PP and PS as carriers and a pigment as an auxiliary material; the pigment is one or more of phthalocyanine blue, phthalocyanine green, fluorescent yellow YG-51 or permanent red F5R.

2. The environment-friendly composite plastic with the pearlescent effect and the multicolor pattern effect as claimed in claim 1, wherein the main material is styrene-butadiene transparent impact-resistant resin.

3. The environment-friendly composite plastic with the pearl effect and the multicolor pattern effect as claimed in claim 1, wherein the auxiliary materials are styrene-methyl methacrylate copolymer, high impact polystyrene and polypropylene.

4. The environment-friendly composite plastic with pearlescent effect and multicolor pattern effect as claimed in claim 1, wherein the polymeric compatibilizer is a graft copolymer of polyolefin and maleic anhydride, an ethylene-octene copolymer and/or a copolymer of styrene and acrylonitrile.

5. The environment-friendly composite plastic with the pearlescent effect and the multicolor pattern effect as claimed in claim 1, wherein the auxiliary agents are 1076, 168, UV-531 and stearic acid.

6. The environment-friendly composite plastic with both pearlescent effect and multicolor pattern effect as claimed in claim 1, wherein the lubricant is calcium stearate, ethylene bis-stearamide and pentaerythritol stearate.

7. The method for preparing the environment-friendly composite plastic with the pearlescent effect and the multicolor pattern effect according to any one of claims 1 to 6, characterized by comprising the following steps:

(1) according to the weight parts, firstly, taking the main material, the auxiliary material and the high molecular compatilizer, stirring at a low speed to uniformly mix the materials until the materials are not adhered to a sheet, a wall or a sediment;

(2) stopping the high-speed stirrer, opening the cover to check that the material is not adhered to a sheet, a wall or deposited on the bottom, adding the uniformly mixed auxiliary agent and lubricant, covering the cover, timing, adjusting the rotating speed, starting stirring, stirring for a certain time, observing the temperature to 40-80 ℃, stopping the machine again, opening the cover to check, and uniformly adhering the powder on the surface of the granular material when the powder is not deposited on the bottom or adhered on the wall to obtain the material of a primary mixing grid;

(4) setting the screw rotating speed of a unit of a twin-screw devolatilization extrusion granulator set and the temperature of a granulator, feeding the materials spread and spread in a primary mixing grid into a co-rotating twin-screw mixing granulator in a manner of cutting from top to bottom in a streamline manner, carrying out melt mixing and extrusion granulation, and feeding the materials along the edge when the materials are added into the extrusion granulator; the double-screw unit is divided into 12 sections of independent temperature control areas, and a normal pressure exhaust port and two vacuum exhaust ports are respectively arranged at 6 sections, 8 sections and 10 sections to ensure that low boiling point substances are vacuum-extracted and volatile matters are reduced to be below 0.2%; finally, the molten material strips extruded from the die head of the extruder enter a cooling water tank and a granulator to obtain environment-friendly composite plastic granules with the diameter of 3x5mm and the effects of pearlescence and multicolor patterns;

8. The method for preparing environment-friendly composite plastic with pearlescent effect and multicolor pattern effect according to claim 7, wherein in the step (1), the rotation speed of stirring is 1000-3500 rpm, and the time is 1-10 min.

9. The method for preparing environment-friendly composite plastic with pearl effect and multicolor pattern effect according to claim 7, wherein in the step (2), the rotation speed of the continuous stirring is 1000-3500 rpm, and the stirring time is 1-10 min.

10. The method for preparing environment-friendly composite plastic with pearlescent effect and multicolor pattern effect according to claim 7, wherein in the step (4), the rotation speed of the screw set is 100-500 rpm; the temperature of the granulator is as follows: the temperature is 150-210 ℃, and the specific temperature rising program is as follows: the temperature of the material is gradually increased from the inlet to 190-210 ℃ from 150 ℃, and then is reduced to 180-200 ℃ of the die.