WO2017215578A1 - Self-reinforced irregularly-shaped section, manufacturing method for same, and applications thereof - Google Patents

Abstract

A self-reinforced irregularly-shaped section, comprising a section and a reinforcing lining provided in a cavity of the section. The section is 100 parts of ASA, SAS, ABS, AS and/or AES sections. The reinforced lining is 5-120 parts of a reinforced styrene-based copolymer composite material. The reinforced styrene-based copolymer composite material comprises the components of: a styrene-based copolymer 20-55 parts; PBT or PMMA 5-30 parts; and a reinforcing agent 30-65 parts. A manufacturing method for the self-reinforced irregularly-shaped section is such that the reinforced styrene-based copolymer composite material is manufactured first, then a main machine and an auxiliary machine designed perpendicular to the main machine are employed for joint extrusion, the main machine is used for extruding the section, the auxiliary machine is used for extruding the reinforced styrene-based copolymer composite material, the main machine and the auxiliary machine extrude concurrently, and the self-reinforced irregularly-shaped section is produced when molded and cooled into form. The self-reinforced irregularly-shaped section prevents the problem of the reinforced lining peeling from the section during transport, mounting, and use, allows low-temperature molding, and has great production stability and molding stability.

Description

Self-reinforced profiled material and preparation method and application thereof Technical field

The invention relates to the technical field of plastic profiles, in particular to a self-reinforced profile material and a preparation method and application thereof.

Background technique

PVC profiles are widely used in building doors and windows, wood-plastic flooring, furniture panels, etc. However, PVC materials themselves have low rigidity and poor resistance to deformation, and steel linings are required when used as door and window materials. Although the traditional metal steel lining can effectively improve the deformation resistance of PVC profiles, the steel lining has the disadvantages of high production energy consumption, poor corrosion resistance, thermal insulation, poor sound insulation, high material density and low welding angle strength. Moreover, when the profile is installed, the process is complicated, and the installer needs to fix the steel lining and the steel profile at the construction site, and the assembly process of the door and window installation is added. Based on this situation, related companies have introduced plastic-based materials to replace traditional steel. The plastic itself has the advantages of good heat insulation, corrosion resistance and light weight. However, the unmodified plastic rigidity is too far from the steel to meet the deformation resistance requirements of the profile.

The use of glass fiber reinforced means can greatly increase the rigidity of the plastic, and provides a solution for this purpose, such as CN 102817529 B, CN 203066745 U, CN 202227876 U, CN 103075071 B and the like, a glass fiber reinforced PBT is disclosed. Any one of carbon fiber reinforced PBT and modified PBT is a reinforcing strip, and a self-reinforced profile material based on PVC material is used instead of the conventional steel lining reinforcing profile. However, in these schemes, the following deficiencies exist: (1) The high temperature co-extrusion of the substrate PVC and the reinforcing strip PBT is likely to cause decomposition and foaming of the PVC substrate, carbonization, thereby causing discoloration of the profile and large odor; (2) reinforcing strip The interface between PBT and substrate PVC is poor. During the transportation, installation and use of the profile, the peeling of the substrate PVC and the reinforcing strip PBT is easy due to collision and bending, which greatly reduces the reinforcing effect of the reinforcing strip. Limit its application. CN 103147664 B discloses a profiled co-extrusion die, which solves the problem of paste and compatibility of PVC by providing a heat insulation layer and an internal rib card groove inside the mold, although the above problems can be partially solved, but the mold cost greatly increase.

Summary of the invention

In order to overcome the above deficiencies of the prior art, it is an object of the present invention to provide a self-reinforcing profile which avoids the problem of peeling of the liner and the profile during transportation, installation and use, and can be formed at a low temperature. With good production stability and molding stability.

Another object of the present invention is to provide a process for the preparation of the above self-reinforced profile.

The invention is achieved by the following technical solutions:

A self-reinforcing profile comprising a profile and a reinforced liner disposed within a profile cavity, the profile being an ASA, SAS, ABS, AS, and/or AES profile, the reinforced liner being a reinforced styrene-based copolymer Composition material, the parts by weight such as under:

ASA, SAS, ABS, AS and / or AES profiles 100 copies

Reinforced styrene-based copolymer composition material 5 parts - 120 parts

Wherein the reinforcing styrene-based copolymer composition material is in parts by weight, and comprises the following components:

Styrene-based copolymer 20-55 parts;

5-30 parts of PBT or PMMA;

Enhancer 30-65 parts;

The adhesion of the ASA, SAS, ABS, AS, and/or AES profiles to the reinforced styrene-based copolymer composition material is 700-1000 N, and the adhesion test uses the following method: ASA, SAS, ABS, AS and / or AES profiles are injection molded into 2mm × 10mm × 100mm splines, then ASA, SAS, ABS, AS and / or AES splines are placed in a 4mm × 10mm × 100mm mold for overmolding reinforced styryl The copolymer composition material was obtained as an adherend of ASA, SAS, ABS, AS and/or AES profiles and reinforced styrene-based copolymer composition materials, and finally the bond strength was tested by a Zwick tensile tester. .

The styrene-based copolymer composition material has an extrusion temperature interval of 160 to 215 °C.

The styrene-based copolymer resin has a melt flow rate of from 1 g/10 min to 80 g/10 min at 220 ° C under a load of 10 kg, which is more easily extruded, preferably from 5 g/10 min to 20 g/10 min, more preferably 10 g/ 10min-15g/10min.

The styrene-based copolymer is selected from the group consisting of styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer ABS, methyl methacrylate-styrene-butadiene-acrylonitrile copolymer MABS, propylene. Nitrile-styrene-acrylate copolymer ASA, acrylonitrile-ethylene propylene diene monomer-styrene copolymer AES, acrylonitrile-silicone rubber-styrene copolymer SAS, methyl methacrylate-styrene copolymer MS One or several of them.

The reinforcing agent is selected from one or more of glass fiber, carbon fiber, basalt fiber, talc powder, wollastonite, whisker, glass microbead, preferably glass fiber, and the glass fiber has a diameter of 6-20 μm.

The styrene-based copolymer composition material of the present invention further comprises, by weight, 0.5-10 parts of a compatibilizing agent, 0.1-5.0 parts of a coupling agent, and 0.1-5.0 parts of a processing aid.

The compatibilizer is selected from the group consisting of styrene-butadiene-acrylonitrile-maleic anhydride copolymer, styrene-butadiene-acrylonitrile-glycidyl methacrylate copolymer, styrene-acrylonitrile-Malay One or more of an acid anhydride copolymer, a styrene-acrylonitrile-glycidyl methacrylate copolymer, an acrylate resin, a methyl methacrylate-styrene copolymer resin, a styrene-maleic anhydride copolymer ;

The coupling agent is selected from one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent; the processing aid includes a lubricant or an anti- One or several of the oxygen agents.

The lubricant is selected from the group consisting of a fatty acid salt, a fatty acid amide, pentaerythritol stearate, a solid paraffin, a liquid paraffin, a stearate, a silicone, an N, N'-ethylene bis stearic acid amide or Several.

The antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] quaternary tetraol and tris[2,4-di-tert-butylphenyl]phosphite a mixture of esters.

The method for preparing a self-reinforced profile according to the present invention comprises the following steps:

(1) Preparation of reinforced styrene-based copolymer composition material: in addition to the reinforcing agent, each raw material of the styrene-based copolymer composition material is added to a high-mixer to be uniformly mixed according to the ratio; and the above mixture is fed into the double In a screw extruder, wherein the reinforcing agent is added through a first vent hole or a side feeding system, and melt extrusion granulation, that is, the styrene-based copolymer composition material is reinforced;

(2) Co-extrusion: co-extrusion preparation is carried out by using a main machine and a vertical machine designed vertically by the main machine. The main machine is used for extruding ASA, SAS, ABS, AS and/or AES profiles, and the auxiliary machine is used for extrusion-reinforced styrene-based The copolymer composition material, the main machine and the auxiliary machine are simultaneously extruded, and the shape is cooled and shaped to obtain a self-reinforced profile.

In the step (1), the mixing temperature is 20-50 ° C, the rotation speed is 100-800 rpm, and the mixing time is 2-5 minutes; the temperature of each section of the twin-screw extruder is 200-240 ° C, double The screw extruder has a length to diameter ratio of 36-48 and a screw speed of 300-500 rpm.

In the step (2), the main machine is a twin-screw extruder, and the temperature of each section of the twin-screw extruder is 150-200 ° C; the auxiliary machine is a single-screw extruder, and the temperature of each section of the single-screw extruder is 160-215 ° C.

Preferably, the main machine is a twin-screw extruder, the head temperature is 175-195 ° C, the temperature of the fuselage one zone is 155-165 ° C, the temperature of the fuselage two zone is 165-175 ° C, and the temperature of the fuselage three zones is 175-185 ° C, the temperature of the four fuselage of the fuselage is 175-185 ° C, the screw speed is 18-22 rpm; the auxiliary machine is a single screw extruder, the head temperature is 175-195 ° C, the temperature of the fuselage area is 160 -165 ° C, the fuselage two zone temperature is 160-175 ° C, the fuselage three zone temperature is 175-185 ° C, the fuselage four zone temperature is 175-185 ° C, the screw speed is 18-22rpm.

The invention also provides the use of the above self-reinforced profile in building doors and windows, wood-plastic flooring or furniture panels.

Compared with the prior art, the present invention has the following advantages:

(1) The reinforcing liner used in the present invention is a reinforced styrene-based copolymer composition material which is an amorphous material, and the profile is made of ASA, SAS, ABS, AS and/or AES profiles, due to the reinforcing lining material and profile. Better compatibility, avoiding the problem of peeling of lining materials and profiles during transportation, installation and use of self-reinforced profiles, and can be widely used in building doors and windows, wood-plastic floors or wall panels;

(2) The reinforced lining material used in the invention can be stably extruded in the temperature range of 160-215 ° C, has a wider processing window, and the lower molding temperature also greatly reduces energy consumption and is more environmentally friendly;

(3) The reinforced lining material used in the present invention has higher melt strength and superior processing and forming properties, thereby Greatly improve the stability of the molding.

(4) Under the condition of providing the same rigidity, the reinforced lining material of the invention has lower density, and the self-reinforced co-extruded profile is lighter in weight, conforming to the light weight and low carbon environmental protection trend advocated by the state.

BRIEF DESCRIPTION OF THE DRAWINGS:

Figure 1 is a photograph of the adherence of the ASA, SAS, ABS, AS, and/or AES profiles to the reinforced liner during the adhesion test.

detailed description

The invention is further described by the following examples in order to provide a better understanding of the invention.

The raw materials used are as follows:

ASA profile, ASA PW-997, Taiwan Chi Mei;

AES profile, AES HW500E, Kumho, South Korea;

AS profile, SAN PN-137H, Taiwan Chi Mei;

ABS profile, ABS AG10NP, Taihua;

SAS profile, DIALAC E259B, UMG Japan;

AS styrene-acrylonitrile resin, SAN PN-137H, Taiwan Chi Mei, melt flow rate 12g/10min;

AS styrene-acrylonitrile resin, SAN NF-5, Taihua custom; melt flow rate 5g/10min;

AS styrene-acrylonitrile resin, SAN NF2200, Taiwan, melt flow rate 35g/10min;

ABS resin, ABS AG10NP, Taiwan; melt flow rate 6g/10min;

PBT resin, PBT 1200-211M, Changchun, Taiwan;

PMMA resin, PMMA CM-205, Taiwan Chi Mei;

ASA styrene-acrylonitrile-acrylate copolymer, ASA PW-997, Taiwan Chi Mei; melt flow rate 5g/10min;

Glass fiber, ECS13-4.5-534A, Tongxiang boulders, 13μm in diameter.

Maleic anhydride styrene copolymer, SMA-700, Shanghai Huawen Company;

Coupling agent, KH560, boiling point chemical industry;

Lubricant, N, N'-ethylene bis stearamide, Shanghai Ningcheng;

Antioxidants, 168 and 1010, Swiss Ciba Specialty Chemicals.

Preparation of reinforced styrene-based copolymer composition materials:

In addition to the reinforcing agent, the raw materials of the styrene-based copolymer composition material are added to the high-mixer to be uniformly mixed according to the ratio of Table 1; the above mixture is fed into a twin-screw extruder, wherein the reinforcing agent passes through the first A vent or side feed system is added, melt extrusion granulation, to enhance the styrene based copolymer composition material. Wherein, the mixing temperature is 20-50 ° C, and the rotation speed is 100-800 rpm, mixing time is 2-5 minutes; the temperature of each section of the twin-screw extruder is 200-240 ° C, the length-to-diameter ratio of the twin-screw extruder is 36-48, and the screw speed is 300- 500 rpm.

The obtained styrene-based copolymer composition material was dried in a blast oven at 90 ° C for 4 hours, and then sampled by Ningbo Haitian injection molding machine BS650-III, and the injection temperature was set to 230-240-240-250 ° C. The properties of the physical property test results of the obtained reinforced styrene-based copolymer composition materials are shown in Table 1.

The tensile strength was tested according to the ISO 527 standard. The sample was a type I specimen and the test equipment was a tensile tester Z020 from Zwick, Germany.

The bending strength was tested according to the ISO 178 standard, the sample size was 4 mm × 10 mm × 80 mm, and the test equipment was the bending test machine Z005 of Zwick Roell, Germany.

The IZOD notched impact strength was tested in accordance with the ISO 180 standard, and the sample size was 4 mm × 10 mm × 80 mm, and the notch depth was 2 mm. The test equipment is the impact tester HIT5.5P from Zwick Roell, Germany.

The density was tested according to the ISO 1183 standard, and the test equipment was a digital liquid density meter MD-300S of Japan ALFA MIRAGE.

Adhesion test: ASA, SAS, ABS, AS and/or AES resin are now injection molded into 2mm × 10mm × 100mm splines, then ASA, SAS, ABS, AS and / or AES splines are placed in 4mm × The lining material was overmolded in a 10 mm x 100 mm mold to obtain an adherend of the ASA, SAS, ABS, AS, and/or AES profiles and the reinforced liner material, as shown in FIG. Finally, Zwick's tensile testing machine was used to test the bond strength to characterize the bond between the reinforced liner and the ASA, SAS, ABS, AS and/or AES profiles.

Table 1 reinforced lining each group distribution ratio (parts by weight) and physical properties

	B1	B2	B3	A1	A2	A3
SAN PN-137H				55	45	35
SMA-700	5	5	5	5	5	5
PBT 1200-211M	65	55	45	10	10	10
ECS13-4.5-534A	30	40	50	30	40	50
KH550	0.5	0.5	0.5	0.5	0.5	0.5
168	0.1	0.1	0.1	0.1	0.1	0.1
1010	0.2	0.2	0.2	0.2	0.2	0.2
N,N-ethylene bis stearamide	0.5	0.5	0.5	0.5	0.5	0.5
Tensile strength (Mpa)	130	143	154	133	147	158
Bending correction (Mpa)	9000	11500	14500	9250	12000	15200
IZOD notched impact strength (kJ/m2)	8.1	8.2	7.8	11.8	13.0	14.4
Density (g/cm3)	1.51	1.62	1.72	1.33	1.43	1.53

Continued Table 1:

It can be seen from Table 1 that the reinforcing lining material of the present invention has more excellent mechanical properties in the case of the same glass fiber content, and in particular, the rigidity is better than that of the reinforced PBT material, and the advantage in plastic-forming steel is more obvious. Secondly, under the condition of providing the same rigidity, the reinforced lining material of the invention has lower density, and the prepared self-reinforced co-extruded profile has a lighter weight, which is in line with the nationally advocated lightweight and low carbon environmental protection trend.

Preparation of self-reinforced profiles:

The main machine is co-extruded with the auxiliary machine vertically designed by the main machine. According to Table 2, the main machine is used for extruding ASA, SAS, ABS, AS and/or AES profiles, and the auxiliary machine is used for extruding the reinforcing lining material. The main machine and the auxiliary machine are simultaneously extruded, and the self-reinforced profile is obtained by cold-cutting after forming;

Wherein, the main machine is a twin-screw extruder, the head temperature is 175-195 ° C, the temperature of the fuselage one zone is 155-165 ° C, the temperature of the fuselage two zone is 165-175 ° C, and the temperature of the fuselage three zones is 175 -185 ° C, the temperature of the fuselage four zones is 175-185 ° C, the screw speed is 18-22 rpm; the auxiliary machine is a single screw extruder, the head temperature is 175-195 ° C, the temperature of the fuselage one zone is 160- At 165 ° C, the temperature in the second zone of the fuselage is 160-175 ° C, the temperature in the three zones of the fuselage is 175-185 ° C, the temperature in the four zones of the fuselage is 175-185 ° C, and the screw speed is 18-22 rpm.

Table 2 Distribution ratios and performance results of each group of self-reinforced profiles (parts by weight)

Continued Table 2:

As can be seen from the data in Table 2, the adhesion of the reinforced PBT material to the ASA, SAS, ABS, AS and/or AES profiles is only about 150 N, while the reinforced lining material of the present invention is used with ASA, SAS, ABS. , the adhesion of AS and / or AES profiles is increased to about 700-1000N, which is 5-6 times that of PBT materials, which means that the reinforced liner of the invention has ASA, SAS, ABS, AS and / or AES profiles Better compatibility, no peeling during the transportation, installation and use of profiles. Secondly, the reinforced PBT material can be plasticized and stabilized in the temperature range of 220-250 ° C, the processing window is narrow and the processing temperature is high, and the reinforced lining material of the invention is plasticized within a wide range of 160-215 ° C. Both are very good and can be extruded stably, which means that the reinforced lining material of the present invention has a wider processing window while being lower The molding temperature also greatly reduces energy consumption and is more environmentally friendly.

Claims (13)

1. A self-reinforced profile characterized by comprising a profile and a reinforcing liner disposed within the profile cavity, the profile being an ASA, SAS, ABS, AS, and/or AES profile, the reinforcing liner being reinforced benzene The vinyl copolymer composition material is in the following parts by weight:

   ASA, SAS, ABS, AS and / or AES profiles 100 copies

   Reinforced styrene-based copolymer composition material 5 parts - 120 parts

   Wherein the reinforcing styrene-based copolymer composition material is in parts by weight, and comprises the following components:

   Styrene-based copolymer 20-55 parts;

   5-30 parts of PBT or PMMA;

   Enhancer 30-65 parts.
2. The self-reinforced profile of claim 1 wherein the adhesion of the ASA, SAS, ABS, AS, and/or AES profiles to the reinforced styrene-based copolymer composition material is from 700 to 1000 N. The adhesion test uses the following method: injection molding ASA, SAS, ABS, AS, and/or AES profiles into 2 mm x 10 mm x 100 mm splines, then placing the ASA, SAS, ABS, AS, and/or AES splines The styrene-based copolymer composition material is overmolded in a mold of 4 mm × 10 mm × 100 mm to obtain an adherend of the ASA, SAS, ABS, AS, and/or AES profiles and the reinforced styrene-based copolymer composition material. Finally, the strength of the bond was tested by Zwick's tensile tester.
3. The self-reinforced profile of claim 1 wherein the reinforced styrene-based copolymer composition material has an extrusion temperature interval of from 160 to 215 °C.
4. The self-reinforcing profile according to claim 1, wherein the styrene-based copolymer has a melt flow rate of from 1 g/10 min to 80 g/10 min, preferably 5 g/10 min at 220 ° C under a load of 10 kg. -20 g/10 min, more preferably 10 g/10 min-15 g/10 min.
5. The self-reinforced profile according to claim 4, wherein the styrene-based copolymer is selected from the group consisting of styrene-acrylonitrile copolymer AS, acrylonitrile-butadiene-styrene copolymer ABS, methacrylic acid. Methyl ester-acrylonitrile-butadiene-styrene copolymer MABS, acrylonitrile-styrene-acrylate copolymer ASA, acrylonitrile-ethylene propylene diene monomer-styrene copolymer AES, acrylonitrile-silicone rubber One or more of styrene copolymer SAS, methyl methacrylate-styrene copolymer MS.
6. The self-reinforced profile according to claim 1, wherein the reinforcing agent is one or more selected from the group consisting of glass fiber, carbon fiber, basalt fiber, talc powder, wollastonite, whisker, and glass microbead. Preferred is glass fiber.
7. The self-reinforcing profile according to claim 6, wherein the glass fibers have a diameter of 6 to 20 μm.
8. A self-reinforced profile according to claim 1 wherein said reinforced styryl group is in parts by weight The copolymer composition material further comprises 0.5-10 parts of a compatibilizer, 0.1-5.0 parts of a coupling agent, and 0.1-5.0 parts of a processing aid.
9. The self-reinforced profile according to claim 8, wherein the compatibilizing agent is selected from the group consisting of styrene-butadiene-acrylonitrile-maleic anhydride copolymer, styrene-butadiene-acrylonitrile-A Glycidyl acrylate copolymer, styrene-acrylonitrile-maleic anhydride copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, acrylate resin, methyl methacrylate-styrene copolymer, One or more of a styrene-maleic anhydride copolymer; the coupling agent is selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. One or more; the processing aid includes one or more of a lubricant or an antioxidant.
10. The method for preparing a self-reinforced profile according to any one of claims 1 to 9, comprising the steps of:

    (1) Preparation of reinforced styrene-based copolymer composition material: in addition to the reinforcing agent, each raw material of the styrene-based copolymer composition material is added to a high-mixer to be uniformly mixed according to the ratio; and the above mixture is fed into the double In a screw extruder, wherein the reinforcing agent is added through a first vent hole or a side feeding system, and melt extrusion granulation, that is, the styrene-based copolymer composition material is reinforced;

    (2) Co-extrusion: co-extrusion preparation is carried out by using a main machine and a vertical machine designed vertically by the main machine. The main machine is used for extruding ASA, SAS, ABS, AS and/or AES profiles, and the auxiliary machine is used for extrusion-reinforced styrene-based The copolymer composition material, the main machine and the auxiliary machine are simultaneously extruded, and the shape is cooled and shaped to obtain a self-reinforced profile.
11. The method for preparing a reinforced profile according to claim 10, wherein in the step (1), the mixing temperature is 20-50 ° C, the rotation speed is 100-800 rpm, and the mixing time is 2-5 minutes. The temperature of each section of the twin-screw extruder is 200-240 ° C, the length-to-diameter ratio of the twin-screw extruder is 36-48, and the screw rotation speed is 300-500 rpm.
12. The method for preparing a self-reinforcing profile according to claim 10, wherein in the step (2), the main machine is a twin-screw extruder, and the temperature of each section of the twin-screw extruder is 150-200 ° C. The auxiliary machine is a single-screw extruder, and the temperature of each section of the single-screw extruder is 160-215 ° C; preferably, the main machine is a twin-screw extruder, the head temperature is 175-195 ° C, and the fuselage area is The temperature is 155-165 ° C, the temperature of the fuselage two zone is 165-175 ° C, the temperature of the fuselage three zones is 175-185 ° C, the temperature of the fuselage four zones is 175-185 ° C, and the screw rotation speed is 18-22 rpm; The machine is a single-screw extruder with a head temperature of 175-195°C, a temperature of 160-165°C in the fuselage area, 160-175°C in the second zone, and 175-185°C in the fuselage. The temperature of the four zones of the fuselage is 175-185 ° C, and the screw speed is 18-22 rpm.
13. Use of the self-reinforced profile of any of claims 1-9 in building doors and windows, wood-plastic flooring or furniture panels.

Images