CN115124806B

CN115124806B - Formula and production process of high-toughness PS plastic coiled material

Info

Publication number: CN115124806B
Application number: CN202211009953.5A
Authority: CN
Inventors: 李木顺
Original assignee: Pulixin Packaging Materials Shanghai Co ltd
Current assignee: Pulixin Packaging Materials Shanghai Co ltd
Priority date: 2022-08-22
Filing date: 2022-08-22
Publication date: 2023-08-25
Anticipated expiration: 2042-08-22
Also published as: CN115124806A

Abstract

The application relates to the field of plastic coiled materials, in particular to a formula of a high-toughness PS plastic coiled material. The raw materials comprise the following components in parts by mass:

Description

Formula and production process of high-toughness PS plastic coiled material

Technical Field

The application relates to the technical field of polystyrene materials, in particular to a formula of a high-toughness PS plastic coiled material and a production process thereof.

Background

Polystyrene coiled material is a common material and is commonly used in the packaging field. The polystyrene has better toughness and processability, stable size and outstanding mechanical and electrical properties, so the polystyrene has wide application.

In order to further improve the mechanical properties of polystyrene coiled materials, modification researches on polystyrene materials are continuously carried out, wherein one scheme is to incorporate whiskers, and the whiskers are a crystal material with high ordered arrangement, and can effectively improve the mechanical strength of polystyrene after being incorporated into raw materials of polystyrene. However, the whisker itself is generally compatible with polystyrene systems, and can lead to reduced transparency of polystyrene coils while improving strength.

Disclosure of Invention

In order to improve the transparency of the polystyrene material after whisker incorporation, the application provides a formula of a high-toughness PS plastic coiled material and a production process thereof.

The application provides a formula of a high-toughness PS plastic coiled material, which comprises the following raw materials in parts by mass:

100 parts of polystyrene

5-20 parts of compatilizer

10 to 15 portions of composite calcium-based whisker

6-10 parts of surfactant

15-25 parts of amino silicone oil

Wherein the composite calcium-based whisker is calcium sulfate whisker and calcium carbonate whisker, and the mass ratio of the calcium sulfate whisker to the calcium carbonate whisker is (0.1-10) to 1.

The amino silicone oil has the main effects in the system that the amino silicone oil can ensure that the components of the whisker and the components of the polystyrene are more uniformly mixed, so that the whisker is easier to disperse in the processing process, and the arrangement regularity of the whisker is improved. Preferably, the viscosity of the aminosilicone is not more than 90cps (25 ℃).

The composite system using the calcium carbonate whisker and the calcium sulfate whisker has better transparency improvement compared with a single whisker. The specific weight of the calcium sulfate whisker and the calcium carbonate whisker is preferably (3-6) to 1. The calcium sulfate whisker may be calcium sulfate hemihydrate or anhydrous calcium sulfate, preferably anhydrous calcium sulfate whisker.

Alternatively, pp random copolymer may be added continuously thereto, allowing for better system compatibility and reduced processing temperatures. The ethylene monomer content in the random pp copolymer is preferably 1 to 2 mole percent.

Optionally, the calcium-based composite whisker is pretreated by a silane coupling agent for improving the bonding strength between an organic phase and an inorganic phase. The silane coupling agents with different brands have better effects, and the silane coupling agent KH-590 is preferable. The mass percentage of the silane coupling agent is not higher than 0.8 percent of the composite calcium-based whisker.

The pretreatment can be carried out in ethanol, acetone or other organic solvents, or can be carried out under the condition of no solvent, if the condition of no solvent is adopted, a mixer can be directly adopted to mix the silane coupling agent and the whisker, so that the silane coupling agent is coated on the surface of the whisker.

Preferably, the compatibilizer is maleic anhydride grafted polyethylene.

In addition, the application also provides a formula and a production process of the high-toughness PS plastic coiled material, and the high-toughness PS plastic coiled material is obtained by mixing the raw materials and then injection molding.

The mixing can be carried out by adopting a high-speed mixer, an internal mixer or other mixing equipment, the temperature of the mixing process is not higher than 205 ℃, the mixture is extruded and sliced by adopting any extruder after the mixing is finished, and the temperature of the extruder is not higher than 205 ℃. Preferably, in the case of pp random copolymer added to the system, the temperature of both the mixing and extrusion processes does not exceed 196 ℃.

Detailed Description

In the present application, polystyrene itself is a copolymer, a homopolymer or any high molecular polymer composed mainly of styrene monomer, wherein the monomer content of styrene is generally considered to be not less than 70%, but a high molecular having a lower styrene monomer content but still exhibiting styrene plastic properties should be considered as polystyrene. In the present application, general-purpose polystyrene or modified polystyrene (e.g., HIPS) may be selected, and in the following examples, commercially available HIPS master batches are selected as the raw materials, but similar effects can still be achieved by using general-purpose polystyrene.

The amino silicone oil in the present application refers to a silicone oil containing an amino group at a terminal group or a side chain of the silicone oil, and particularly to a silicone oil containing an amino group at a side chain.

The surfactant may be any one or a mixture of several of cationic surfactant, anionic surfactant, nonionic surfactant and zwitterionic surfactant which does not damage the whole polystyrene structure.

Besides the components described in the examples, other auxiliary agents such as preservative, anti-ultraviolet agent, colorant, brightening agent, leveling agent, reinforcing agent, toughening agent and the like can be added into the system, and in principle, the mass fraction of single auxiliary agent is not more than 1%, and the total mass fraction of all auxiliary agents is not more than 5%.

The prepared sample was subjected to measurement of properties by the following method.

In the following examples and preparations, samples were prepared as corresponding film samples for measurement.

The tensile strength and elongation at break of the above film were measured by the test method of the tensile properties of a plastic film of GB/13022-1991, the pattern length was 90cm, and the test speed was 200mm/min.

Referring to the national standard GB/T8809-2015 plastic film anti-pendulum impact test method, a sample is a circular sheet with the diameter of 100mm and the thickness of 0.25 mm; the impact resistance of the sample was measured.

With reference to GB/T37841-2019 plastic films and sheet puncture resistance test methods, puncture resistance of film samples was measured, puncture speed was 100mm/min, sample size was 25mm by 25mm, and thickness was 0.25mm.

The transmittance of the sample was measured by referring to the measurement of the transmittance and haze of the transparent plastic of national standard GB/T2410-2008, the sample was a wafer with a diameter of 50mm and a thickness of 0.25mm, and the measurement was performed by a spectrophotometry.

Detailed description of the application

Examples 1 to 14 and comparative examples 1 to 5 each relate to polystyrene coiled materials, and the mass ratio of the raw materials is shown in Table 1.

Table 1, examples 1 to 14 and comparative examples 1 to 5, the mass ratios of the components

In the above examples and comparative examples, the polystyrene was a commercially available HIPS master batch, the aminosilicone viscosity was 100cps (25 ℃ C.), the calcium sulfate whiskers were anhydrous calcium sulfate, the molar content of ethylene monomer in the random pp copolymer was 1.4%, the surfactant was carboxymethyl cellulose ether, and the compatibilizer was a commercially available maleic anhydride grafted polyethylene type compatibilizer

The preparation steps of the polyethylene coiled material are as follows:

1. mixing: adding the raw materials into a high-speed mixer, and mixing for 15min at 202 ℃;

2. melt extrusion: melting and extruding the mixed raw materials by a double-screw extruder, wherein the temperatures of three sections in the double-screw extruder are respectively 200 ℃, 204 ℃ and 202 ℃, and the temperature of an extrusion head is controlled to be not higher than 205 ℃;

3. and drawing and cooling the extruded film, and cutting to obtain a sample.

Example 15 differs from example 3 in that calcium sulfate whiskers are calcium sulfate hemihydrate.

Example 16 differs from example 3 in that the amino silicone oil has a viscosity of 250cps (25 ℃).

Example 17 differs from example 3 in that the amino silicone oil has a viscosity of 150cps (25 ℃).

Example 18 differs from example 12 in that the vinyl monomer molar content of the random pp copolymer is 1.0%.

Example 19 differs from example 12 in that the vinyl monomer molar content of the random pp copolymer is 2.0%.

Example 20 differs from example 12 in that the vinyl monomer molar content of the random pp copolymer is 4.0%.

Example 21 differs from example 12 in that the mass of the random pp copolymer and the like is replaced with the ordinary pp.

Example 22 differs from example 14 in that in step 1, the composite calcium-based whiskers were mixed with the silane coupling agent in a high-speed mixer for 30min, and then the other raw materials were added for further mixing for 15min. Wherein the silane coupling agent is KH570, and the mass ratio of the silane coupling agent to the composite calcium-based whisker is 0.008:1.

Example 23 differs from example 14 in that in step 1, the composite calcium-based whiskers were mixed with the silane coupling agent in a high-speed mixer for 30min, and then the other raw materials were added for further mixing for 15min. Wherein the silane coupling agent is KH570, and the mass ratio of the silane coupling agent to the composite calcium-based whisker is 0.004:1.

Example 24 differs from example 14 in that in step 1, the composite calcium-based whiskers were mixed with the silane coupling agent in a high-speed mixer for 30min, and then the other raw materials were added for further mixing for 15min. Wherein the silane coupling agent is KH570, and the mass ratio of the silane coupling agent to the composite calcium-based whisker is 0.012:1.

In addition, the following comparative examples were set.

Comparative example 6 amino silicone oil was replaced with an equal mass of a common silicone oil, which was 150scp of a general purpose silicone oil.

The experimental results of the above examples and comparative examples are shown in table 2.

Table 2, experimental data for examples and comparative examples

Project	Tensile Strength	Elongation at break	Impact strength	Puncture resistance	Transmittance of light
						Unit (B)	mpa	％	KJ/m2	N	(％)
Example 1	53.0	56.4	16.0	0.94	83.1
						Example 2	53.7	55.9	16.1	0.93	82.6
Example 3	53.6	55.3	16.1	0.93	82.4
						Example 4	53.4	54.8	16.2	0.93	82.0
Example 5	51.0	52.1	14.8	0.89	80.4
						Example 6	51.2	52.4	15.0	0.87	80.3
Example 7	55.8	57.8	15.9	0.95	85.9
						Example 8	55.5	58.5	16.1	0.94	84.7
Example 9	53.4	55.0	15.2	0.89	83.2
						Example 10	53.2	54.6	15.1	0.89	82.7
Example 11	53.2	60.1	16.2	0.94	84.4
						Example 12	53.3	59.8	16.3	0.93	84.1
Example 13	53.4	60.3	16.2	0.93	84.6
						Example 14	56.0	65.9	16.0	0.94	87.1
Example 15	51.9	54.8	15.6	0.90	80.7
						Example 16	53.3	56.0	16.1	0.94	79.4
Example 17	53.2	56.8	15.9	0.93	84.0
						Example 18	53.5	60.4	16.2	0.95	83.8
Example 19	53.1	59.9	16.0	0.94	84.6
						Example 20	53.4	59.6	16.3	0.93	81.7
Example 21	52.1	57.8	16.4	0.82	80.0
						Example 22	58.3	63.6	17.2	1.03	90.7
Example 23	58.6	63.9	17.4	1.05	90.3
						Example 24	58.8	63.7	17.4	1.05	86.5
Comparative example 1	47.2	53.5	16.2	0.92	72.3
						Comparative example 2	44.3	51.0	15.9	0.88	74.7
Comparative example 3	48.9	55.7	16.4	0.92	70.3
						Comparative example 4	45.0	48.6	15.8	0.92	73.8
Comparative example 5	47.1	50.3	16.0	0.92	64.0
						Comparative example 6	45.4	48.2	15.5	0.90	73.2

As can be seen from the comparison of examples 1 to 4 and comparative examples 1 to 6, the technical scheme of the application can ensure that the polystyrene coiled material has stronger strength, puncture resistance and impact resistance, and simultaneously maintains better transparency, thereby avoiding adverse effects on the polystyrene coiled material caused by whisker doping. The effect is most obvious, the whisker is not easy to disperse in the processing process after the compatilizer is lacked, the whisker is not tightly connected with the polystyrene material, and more white spots are easy to be formed on the surface of the polystyrene coiled material.

The amino silicone oil can guide the polarity in the whisker through an amino active group in the system and is filled between the whisker and a polystyrene system, so that the effects of obviously improving the transparency and the strength are achieved. In comparative example 6, the conventional silicone oil had poor adsorptivity to whiskers and failed to exert a similar effect. In addition, in the additional experiment, even after the composite whisker is modified by the coupling agent, the effect of the amino silicone oil is still obviously stronger than that of the common silicone oil. Further, as is clear from comparison with examples 16 and 17, an excessive viscosity of the aminosilicone resulted in deterioration of the fluidity of the system, and the aminosilicone itself was difficult to uniformly disperse, but adversely affected the polystyrene coil.

The use of composite calcium-based whiskers has significantly stronger transparency and strength than the use of single whiskers. In general, the strength of the calcium sulfate whisker is stronger than that of the calcium carbonate whisker, and the reason for adopting the consistent whisker to have better performance is probably that different whiskers have different strength, modulus and charge arrangement, so that the components are not easy to agglomerate when most of the volume of the system is occupied by organic polymers, and can be more uniformly dispersed in the system.

In examples 11 to 14 and 18 to 21, a random PP copolymer is added, and the random PP copolymer has a soft characteristic, so that the components can be uniformly mixed at about 200 ℃, and the strength and the transparency of the prepared polystyrene coiled material can be further improved while the processability in the system can be good. Wherein, the content of the vinyl monomer has a certain influence, and the random PP copolymer with the excessively high content of the vinyl monomer or the common PP has a difficult effect of enhancing the fluidity in a system, and the strengthening of the final product is not as good as that of the random PP copolymer with the molar content of the vinyl monomer of 1-2 percent.

In examples 22 to 24, the composite calcium-based whiskers were further modified, and after modification with the coupling agent, the strength was significantly improved, and at the same time, the overall arrangement was more uniform due to the improved bonding strength between the calcium-based fibers and the silicone oil, and the transparency of the polystyrene film was further improved.

The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.

Claims

1. The high-toughness PS plastic coiled material is characterized by comprising the following raw materials in parts by mass:

200 parts of polystyrene

5-20 parts of compatilizer

10 to 15 portions of composite calcium-based whisker

6-10 parts of surfactant

15-25 parts of amino silicone oil

Wherein the composite calcium-based whisker is calcium sulfate whisker and calcium carbonate whisker, and the mass ratio of the calcium sulfate whisker to the calcium carbonate whisker is (0.1-10) to 1;

the compatilizer is maleic anhydride grafted polyethylene; the kinematic viscosity of the amino silicone oil is not higher than 150cps (25 ℃).

2. The high-toughness PS plastic coiled material according to claim 1, wherein the raw material further comprises 4-8 parts by mass of pp random copolymer.

3. The high toughness PS plastic coil as claimed in claim 2, wherein the random pp copolymer has a molar content of ethylene monomer of 1-2%.

4. The high-toughness PS plastic coiled material according to claim 1, wherein the mass ratio of the calcium sulfate whisker to the calcium carbonate whisker is (3-6) to 1.

5. A high toughness PS plastic coil according to claim 1, wherein both the calcium sulfate whiskers and the calcium carbonate whiskers are pretreated with a coupling agent.

6. A high toughness PS plastic coil according to claim 5, wherein the calcium sulfate whiskers are anhydrous calcium sulfate whiskers.

7. The high-toughness PS plastic coiled material according to claim 5, wherein a silane coupling agent is selected in the pretreatment process of the coupling agent, and the mass of the silane coupling agent is not higher than 0.8% of the mass of the composite calcium-based whisker.

8. The process for producing a high-toughness PS plastic coil stock according to any one of claims 1 to 7, wherein the raw materials are mixed and then extrusion-molded, and wherein the heating temperature is not higher than 205 ℃ during the mixing and extrusion.