A syndiotactic polystyrene and a method for preparing the same, a resin composition, an article, and an application

Abstract

This invention provides syndiotactic polystyrene, its preparation method, resin composition, articles, and applications. The preparation method of the syndiotactic polystyrene includes: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst and a mixture of saturated hydrocarbons to obtain the syndiotactic polystyrene; the mass percentage of the saturated hydrocarbon mixture in the syndiotactic polystyrene is 0.5% to 5%. The syndiotactic polystyrene obtained by the preparation method of this invention exhibits excellent color uniformity, providing a more uniform dispersion matrix for the introduction of antioxidants and other additives in subsequent processing, improving the dispersion uniformity of additives, and without affecting the mechanical properties of the syndiotactic polystyrene, and without causing an increase in mold fouling during processing.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a syndiotactic polystyrene, its preparation method, resin composition, products and applications. Background Technology

[0002] Syntactic polystyrene (sPS) is a high-performance polymer with special stereoregularity. Due to its excellent crystallization rate, mechanical strength, chemical stability and good processability, it has shown broad application prospects in many high-end industrial fields such as automotive parts and electronic packaging materials.

[0003] To obtain products with superior performance, functional additives are typically added during the post-polymerization treatment stage in practical applications, followed by melt blending to obtain syndiotactic polystyrene particles. For example, syndiotactic polystyrene and antioxidants can be dispersed through melt blending during the granulation stage. While this process is widely used, it also has drawbacks. It's difficult to achieve highly uniform dispersion of trace amounts of additives during post-treatment, potentially leading to performance limitations. Furthermore, excessive addition to compensate for uneven dispersion can cause precipitation and other problems, resulting in poor color uniformity of the syndiotactic polystyrene particles.

[0004] Therefore, developing a preparation process for syndiotactic polystyrene that can improve the color uniformity of materials and facilitate the uniform dispersion of additives is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide syndiotactic polystyrene, its preparation method, resin composition, products, and applications. The syndiotactic polystyrene prepared by the aforementioned process exhibits excellent color uniformity, providing a more uniform dispersion matrix for the introduction of antioxidants and other additives during subsequent processing, thus improving the dispersion uniformity of the additives. Simultaneously, the syndiotactic polystyrene possesses good mechanical properties, and mold fouling does not increase during processing.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing syndiotactic polystyrene, the method comprising: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst and a mixture of saturated hydrocarbons to obtain the syndiotactic polystyrene; wherein the syndiotactic polystyrene contains a mixture of saturated hydrocarbons; and wherein the mass percentage of the mixture of saturated hydrocarbons in the syndiotactic polystyrene is 0.5% to 5%.

[0007] In this invention, by adding a saturated hydrocarbon mixture during the polymerization stage, the viscosity of the system can be reduced, mass transfer and heat dissipation can be improved, polymer adhesion can be reduced, and particle formation can be promoted. This not only helps to improve the color uniformity of the product and provides a more uniform dispersion matrix for the introduction of antioxidants and other additives in subsequent processing, but also plays an internal lubricating role, reducing the heat generated inside the reactor due to stirring and material friction, and improving process safety and operational controllability. At the same time, it improves powder flowability, reduces the adhesion and agglomeration tendency between powders, prevents the "bridging" phenomenon in the hopper during the discharge process, and ensures the stability and smoothness of continuous production. In addition, it has virtually no impact on the mechanical properties and processing performance of the material (it will not lead to an increase in mold fouling during subsequent processing).

[0008] In this invention, the content of the saturated hydrocarbon mixture in the syndiotactic polystyrene is based on the mass of the added raw materials. Taking the mass of the added saturated hydrocarbon mixture and styrene as 100%, the mass of the added saturated hydrocarbon mixture is 0.5% to 5%.

[0009] In this invention, if the content of the saturated hydrocarbon mixture is too high, it will dilute the reactants, thereby inhibiting the reactivity, leading to a decrease in molecular weight, cessation of polymerization, or stickiness and decreased mechanical properties of the product; if the content is too low, the color uniformity of syndiotactic polystyrene will deteriorate, and the dispersibility will be poor when blended with additives.

[0010] In this invention, the saturated hydrocarbon mixture includes a mixture of at least two of saturated straight-chain alkanes, saturated branched alkanes, and cycloalkanes; the saturated hydrocarbons have ≥10 carbon atoms, for example, 14 to 36 carbon atoms.

[0011] In this invention, the mass percentage of the saturated hydrocarbon mixture in the syndiotactic polystyrene is 0.5% to 5%, for example, it can be 0.55%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, or any of the above values, more preferably 1% to 3%.

[0012] Preferably, the saturated hydrocarbon mixture includes white oil.

[0013] Preferably, the kinematic viscosity of the saturated hydrocarbon mixture at 40°C is 6.1~16.5 mm. 2 / s, for example, can be 6.2mm 2 / s, 6.5 mm 2 / s, 6.8 mm 2 / s, 7 mm 2 / s, 7.2 mm 2 / s, 7.5 mm 2 / s, 7.8 mm 2 / s, 8 mm 2 / s, 8.2 mm 2 / s, 8.5 mm 2 / s, 8.8 mm 2 / s, 9 mm 2 / s, 9.2 mm 2 / s, 9.5 mm 2 / s, 9.8 mm 2 / s, 10 mm 2 / s, 10.2 mm 2 / s, 10.5 mm 2 / s, 10.8 mm 2 / s, 11 mm 2 / s, 11.2 mm 2 / s, 11.5 mm 2 / s, 11.8 mm 2 / s, 12 mm 2 / s, 12.2mm 2 / s, 12.5 mm 2 / s, 12.8 mm 2 / s, 13 mm 2 / s, 13.2 mm 2 / s, 13.5 mm 2 / s, 13.8 mm 2 / s, 14 mm 2 / s, 14.2 mm 2 / s, 14.5 mm 2 / s, 14.8 mm 2 / s, 15 mm 2 / s, 15.2 mm 2 / s, 15.5 mm 2 / s, 15.8 mm 2 / s, 16mm 2 / s, 16.2 mm 2 / s or any of the above values, more preferably 9.0~11.0mm 2 / s.

[0014] In this invention, the catalyst comprises the following components: (A) Titanocene metal compounds; (B) Alkyl aluminum oxane b1, and / or compound b2 that can react with titanium metal compounds to form ionic complexes; (C) Organoaluminum compounds.

[0015] In this invention, the saturated hydrocarbon mixture can be added to the polymerization reactor before the catalyst and styrene are introduced, or it can be mixed with the catalyst or styrene monomer before the catalyst comes into contact with styrene.

[0016] Preferably, the general formula of component (A) is R 1 TiX 1 X 2 X 3 .

[0017] Among them, R 1 Selected from any one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or fused polycyclic cyclopentadienyl containing at least one saturated ring; X 1 X 2 and X 3 Each of the substituents is independently selected from any one of hydrogen atom, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkylsilyl, C6-C20 aryl, C6-C20 aryloxy, C7-C20 arylalkyl, and halogen atom; the substituents include at least one of halogen atom, C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C6-C20 arylsilyl, and C7-C20 arylalkyl, and when the number of substituents is greater than 1, the substituents may be the same or different.

[0018] In this invention, the C1-C12 alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group, and exemplary examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-decyl, etc.; the same expressions in the following text have the same meaning.

[0019] In this invention, the C1~C12 alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentoxy, n-hexoxy, and n-decoxy; the same expressions in the following text have the same meaning.

[0020] In this invention, C6-C20 aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthracene, etc.; the same expressions in the following text have the same meaning.

[0021] In this invention, C6~C20 aryloxy groups refer to groups formed by replacing one H with O in the aforementioned C6~C20 aryl groups; the same expressions below have the same meaning.

[0022] In this invention, C7~C20 aralkyl refers to a group formed by replacing at least one H in the aforementioned C6~C20 aryl groups with an alkyl group; the same expression below has the same meaning.

[0023] In this invention, C1~C12 alkylsilyl groups can be, for example, C1, C2, C4, C6, C8, C10, or C11 alkylsilyl groups; the alkylsilyl group refers to a group formed by replacing at least one H in a silane with an alkyl group; the same expressions in the following text have the same meaning; wherein, the linking site can be in an alkyl group or in a silyl group.

[0024] In this invention, C6~C20 arylsilyl groups can be, for example, C8, C10, C14, C16, or C18 arylsilyl groups; the arylsilyl group refers to a group formed by replacing at least one H in a silane with an aryl group; the same expressions in the following text have the same meaning; wherein, the linking site can be in the aryl group or in the silyl group.

[0025] In this invention, the halogen atoms include F, Cl, Br, and I.

[0026] In this invention, the number of substituents in "substituted or unsubstituted" is ≥1. When the number of substituents is greater than 1, the substituents can be the same or different.

[0027] In this invention, component (A) includes cyclopentadienyltriethyltitanium, cyclopentadienyltributyltitanium, cyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltributyltitanium, cyclopentadienyltrimethoxytitanium, cyclopentadienyltriethoxytitanium, pentamethylcyclopentadienyltrimethoxytitanium, pentamethylcyclopentadienyltrichloride, cyclopentadienyltriphenoxytitanium, cyclopentadienylmonophenoxytitanium dichloride, cyclopentadienyltribenzyltitanium, and cyclopentadienyltrimethyltitanium. At least one of the following: dibenzyl titanium, indene trichloride titanium, indene trimethoxy titanium, indene trimethyl titanium, indene tribenzyl titanium, octahydrofluorenyl trimethoxy titanium, 9-isopropyl-octahydrofluorenyl trimethoxy titanium, 4,5,6,7-tetrahydroindene trimethoxy titanium, 1,2,3,4-tetramethyl-octahydrofluorenyl trimethoxy titanium, 1-trimethylsilyl-2-methyl-4,5,6,7-tetrahydroindene trimethoxy titanium, and 1-dimethylphenylsilyl-2-methyl-4,5,6,7-tetrahydroindene trichloride titanium.

[0028] Preferably, the alkylaluminoxane b1 is selected from C1-C8 straight-chain alkylaluminoxanes.

[0029] In this invention, the alkylaluminoxane b1 is a reaction product of C1~C8 straight-chain alkylaluminum and water.

[0030] In this invention, the alkylaluminoxane b1 includes at least one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, n-pentylaluminoxane, n-hexylaluminoxane, and n-heptylaluminoxane.

[0031] Preferably, the general formula of compound b2 is: .

[0032] Among them, R 2 At least one alkyl group selected from the group having ≥1 carbon atom (e.g., 1, 2, 4, 6, 8, 10, 12 or any range thereof) and the group having ≥6 carbon atom (e.g., 6, 8, 10, 12, 14, 16, 18, 20 or any range thereof), R 2 Same or different; M is selected from at least one of B, Al, Si, P, and As; X 4 The radical is selected from at least one of C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C7-C20 aralkyl, and C6-C20 haloaryl, where q is an integer from 2 to 8, for example, it can be 3, 4, 5, 6, 7 or any value between the above, and X. 4 Same or different.

[0033] In this invention, compound b2 includes at least one of triphenylmethyltetraphenylborate, triphenylmethyl-tetra(pentafluorophenyl)borate, tri(2,4,6-trimethylphenyl)methyltetra(pentafluorophenyl)borate, and triphenylmethyltetra(3,5-bistrifluoromethylphenyl)borate.

[0034] Preferably, the general formula of the component (C) is R 3 p AlH 3-p .

[0035] Among them, R 3 Selected from C1-C8 alkyl groups, which can be straight-chain alkyl groups or branched alkyl groups, such as C1, C2, C3, C4, C5, C6, C7, and C8 alkyl groups, including but not limited to methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, n-pentyl, and n-hexyl; 0 ≤ p ≤ 3, for example, 0, 1, 2, and 3; when p > 1, R 3 Same or different.

[0036] In this invention, component (C) includes at least one of triisobutylaluminum, trimethylaluminum, triethylaluminum, triisopropylaluminum, diisobutylaluminum hydride, tri-n-butylaluminum, tri-n-hexylaluminum, di-n-butylaluminum, diisopropylaluminum, and n-butylaluminum.

[0037] Preferably, the molar ratio of aluminum to the titanoceramic metal compound in the alkylaluminoxane b1 is (10~1000):1; wherein, the specific value in (10~1000) can be, for example, 20, 40, 60, 800, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or any range between the above values.

[0038] Preferably, the molar ratio of M to the titanium metal compound in compound b2 is (0.5~1.5):1; wherein the specific value of (0.5~1.5) can be, for example, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45 or any range of the above values.

[0039] Preferably, the molar ratio of aluminum to titanium metal compound in component (C) is (10~1000):1; wherein the specific value of (10~1000) can be, for example, 20, 40, 60, 800, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or any range between the above values.

[0040] In this invention, the contact order of the catalyst components is not particularly limited. A catalyst solution can be prepared by mixing components (A) and (B), and optionally component (C), in a suitable solvent to dilute the catalyst. The solvent may be, for example, toluene and / or ethylbenzene. Exemplarily, the catalyst preparation method includes: mixing components (B) and (C) separately with a solvent to obtain component (B) solution and component (C) solution with a concentration of 1-3 mmol / mL; and mixing component (A), component (B) solution, and component (C) solution according to the formulation amount to obtain the catalyst.

[0041] In this invention, the contact temperature (i.e., mixing temperature) of each component of the catalyst is 0℃~100℃, and they are in contact in an inert atmosphere such as nitrogen or argon.

[0042] Preferably, the concentration of the titanoceramic metal compound relative to styrene is 1 × 10⁻⁶. -7 ~5×10 -4 mol / L, for example, 2×10 -7 4×10 -7 6×10 -7 8×10 -71×10 -6 2×10 -6 4×10 -6 6×10 -6 8×10 -6 1×10 -5 2×10 -5 4×10 -5 6×10 -5 8×10 -5 1×10 -4 2×10 -4 4×10 -4 Or any of the above values; more preferably 5 × 10 -6 ~2×10 -4 mol / L, more preferably 1×10 -5 ~1×10 -4 mol / L.

[0043] Preferably, the reaction is carried out in a nitrogen-hydrogen mixture.

[0044] Preferably, the reaction is carried out in a nitrogen-hydrogen mixture, wherein the volume fraction of hydrogen in the nitrogen-hydrogen mixture is 0.1% to 20%, for example, it can be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any range between the above values.

[0045] Preferably, the reaction temperature is 0℃~100℃, for example, it can be 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or any of the above values.

[0046] Preferably, the reaction pressure is 0 MPa to 10 MPa, for example, it can be 0 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa or any range between the above values.

[0047] In this invention, the pressure is measured using an apparent pressure gauge.

[0048] Preferably, the preparation method includes batch polymerization.

[0049] In this invention, the reaction time is 1 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours or any of the above values.

[0050] In this invention, after the reaction is completed, a devolatilization step is also included; the devolatilization method includes: raising the temperature to 110~130℃ at a rate of 0.5~5℃ / min, and increasing the vacuum to -0.1MPa at a rate of 1~3kPa / min to carry out devolatilization.

[0051] In a second aspect, the present invention provides a syndiotactic polystyrene, wherein the syndiotactic polystyrene is prepared by the preparation method described in the first aspect.

[0052] In this invention, the melt index of the syndiotactic polystyrene is preferably 1~35 g / 10 min.

[0053] In this invention, the melt index of the syndiotactic polystyrene was tested according to the ISO 1133-1:2022 standard method at 300°C and under a 1.2 kg load.

[0054] In this invention, the weight-average molecular weight of the syndiotactic polystyrene is more preferably 1.2 × 10⁻⁶. 5 g / mol ~ 2.8 × 10 5 g / mol.

[0055] In this invention, the weight-average molecular weight of the syndiotactic polystyrene was determined using gel permeation chromatography (GPC-IR, Polymer Char, Spain, equipped with dual infrared and viscosity detectors). A high-temperature GPC-IR system was used, with 1,2,4-trichlorobenzene as the mobile phase, a flow rate of 1.0 mL / min, a column temperature of 160°C, a detector temperature of 160°C, and an injector temperature of 160°C. A calibration curve was established using polystyrene standards (weight-average molecular weight range: 266-12,900,000 g / mol). The sample was dissolved in trichlorobenzene (concentration 0.125 mg / mL), and the injection volume was 200 μL. The data were processed using GPC ONE software to obtain the weight-average molecular weight (Mw).

[0056] Thirdly, the present invention provides a resin composition comprising syndiotactic polystyrene and an additive; the syndiotactic polystyrene is prepared by the preparation method described in the first aspect.

[0057] In this invention, the mass percentage of the resin composition containing meso-polystyrene is ≥20%, for example, it can be ≥50%, ≥70%, ≥90%, etc.

[0058] Preferably, based on 100 parts by weight of syndiotactic polystyrene, the mass of the additive is 0.01 to 20 parts, for example, 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or any range of the above values.

[0059] Preferably, the other additives include at least one of antioxidants, lubricants, crosslinking agents, crosslinking aids, nucleating agents, plasticizers, flame retardants, colorants, antistatic agents, and compatibilizers.

[0060] In this invention, other functional components, such as a second resin and fillers, may be added to the resin composition as needed.

[0061] In this invention, the mass of the second resin is 0 to 60 parts, based on 20 to 100 parts of syndiotactic polystyrene. For example, it can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, or any range of the above values. The mass of the filler is 0 to 50 parts, for example, it can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, or any range of the above values.

[0062] In this invention, the filler includes at least one of fibrous filler, granular filler, and powdered filler.

[0063] In this invention, the fibrous filler includes at least one of glass fiber, carbon fiber, whiskers, ceramic fiber, and metal fiber.

[0064] In this invention, the granular filler and powdered filler are each independently selected from at least one of talc, carbon black, graphite, titanium dioxide, silicon dioxide, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, tin oxide, aluminum oxide, kaolin, silicon carbide, metal powder, glass powder, glass flakes, and glass microspheres.

[0065] In this invention, when the filler is selected from glass fillers, the glass used includes at least one of E glass, C glass, S glass, D glass, ECR glass, A glass, AR glass, boron-free glass, and fluorine-free glass.

[0066] In this invention, the length of the glass fiber is 0.05 mm to 50 mm, for example, it can be 0.1 mm, 0.5 mm, 1 mm, 2 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm or any of the above values; the diameter is 5 μm to 20 μm, for example, it can be 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm or any of the above values.

[0067] In this invention, the second resin comprises polyamide, more preferably at least one of polycaprolactam (PA6), polyhexamethylene adipamide (PA66), polyundecanoamide (PA11), polydodecanoamide (PA12), polyhexamethylenediamine sebacate amide (PA610), polyhexamethylenediamine dodecanoic acid amide (PA612), polydecanediamine sebacate amide (PA1010), polydodecanoic acid sebacate (PA1012), polydodecanediamine dodecanoic acid amide (PA1212), polyhexamethylenediamine terephthalamide (PA-6T), polynonadiamine terephthalamide (PA-9T), and polydecanediamine terephthalamide (PA-10T).

[0068] In this invention, the compatibilizer includes modified styrene-based polymers and / or modified polyphenylene ether-based polymers.

[0069] In this invention, the modified styrene-based polymers include at least one of the following: styrene-maleic anhydride copolymer, styrene-glycidyl methacrylate copolymer, terminal carboxylic acid modified polystyrene, terminal epoxy modified polystyrene, terminal oxazoline modified polystyrene, terminal amine modified polystyrene, sulfonated polystyrene, styrene-based ionomers, styrene-methyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate terpolymer, acrylate-styrene copolymer, styrene-b-glycidyl methacrylate-b-styrene, polybutylene terephthalate-g-polystyrene, maleic anhydride modified syndiotactic polystyrene, fumaric acid modified syndiotactic polystyrene, glycidyl methacrylate modified syndiotactic polystyrene, and amine modified syndiotactic polystyrene.

[0070] In this invention, the modified polyphenylene ether polymer includes at least one selected from styrene-maleic anhydride-polyphenylene ether graft polymer, maleic anhydride modified polyphenylene ether, fumaric acid modified polyphenylene ether, glycidyl methacrylate modified polyphenylene ether, and amine modified polyphenylene ether.

[0071] In this invention, the polyphenylene ether in the modified polyphenylene ether polymer includes poly(2,6-dimethyl-1,4-phenylene ether), poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4′-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl- At least one of 6-phenyl-1,4-phenylene ether, poly(2-phenyl-1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and poly(2,6-diethyl-1,4-phenylene ether).

[0072] In this invention, the grafting rate of maleic anhydride in the maleic anhydride-modified polyphenylene ether is 0.5% to 5%; the grafting rate of fumaric acid in the fumaric acid-modified polyphenylene ether is 0.5% to 5%; and the grafting rate is the mass fraction of the grafting monomer relative to the modified polyphenylene ether.

[0073] In this invention, the modified polyphenylene ether polymer can be prepared by polyphenylene ether and a modifier; specifically, it includes: in the presence of an initiator, polyphenylene ether and a modifier are melt-blended on an extruder at a temperature of 250°C to 350°C to obtain the modified polyphenylene ether polymer.

[0074] In this invention, the antioxidants include, but are not limited to, primary antioxidants, such as any one or a combination of at least two of the following: 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(4-methyl-6-nonylphenol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate); and secondary antioxidants, such as tri(nonylphenyl) phosphite and / or dilauryl thiodipropionate.

[0075] In this invention, the lubricant includes, but is not limited to, at least one of ethylene bis-stearamide (EBS), glyceryl monostearate, oleamide, and erucamide.

[0076] In this invention, the crosslinking agent includes, but is not limited to, dicumyl peroxide, benzoyl peroxide, divinylbenzene, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, etc.

[0077] In this invention, the crosslinking aids include, but are not limited to, triallyl isocyanurate, trimethylolpropane trimethacrylate, etc.

[0078] In this invention, the nucleating agent includes, but is not limited to, any one or a combination of at least two of the following: organophosphate nucleating agents, organophosphate metal salt nucleating agents, sorbitol nucleating agents, and carboxylic acid metal salt nucleating agents.

[0079] In this invention, the plasticizers include, but are not limited to, dioctyl phthalate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate, and epoxidized soybean oil.

[0080] In this invention, the flame retardant includes, but is not limited to, ammonium polyphosphate, melamine cyanurate, triphenyl phosphate, resorcinol bisphenyl phosphate, phosphazene compounds, zinc borate, zinc oxide, aluminum hydroxide, antimony trioxide, and organic aluminum phosphonates.

[0081] In this invention, the antistatic agent includes, but is not limited to, quaternary ammonium salt antistatic agents, fatty acid ester antistatic agents, etc.

[0082] In this invention, the method for preparing the resin composition includes: mixing syndiotactic polystyrene and optionally fillers, a second resin, a compatibilizer, and additives, and extruding to obtain the resin composition.

[0083] Fourthly, the present invention provides an article formed by molding syndiotactic polystyrene prepared by the preparation method described in the first aspect, or syndiotactic polystyrene as described in the second aspect, or a resin composition as described in the third aspect.

[0084] In this invention, the molding methods include, but are not limited to, injection molding, blow molding, vacuum forming, and extrusion molding.

[0085] In this invention, the products include, but are not limited to, household goods, electronic components, household appliances, gardening equipment, medical technology equipment, and motor vehicle parts; for example, the household goods include, but are not limited to, food containers, tableware, food storage boxes, bathroom fixtures, shelves, storage boxes, wardrobes, cabinets, lamp housings, and blinds; the electronic components include, but are not limited to, SMT components, capacitors, transformers, LED lamp covers, and computer housings; the household appliances include, but are not limited to, rice cookers, microwave ovens, coffee machines, air conditioners, washing machines, refrigerators, and vacuum cleaners; the gardening equipment includes, but is not limited to, water pump impellers, etc. Valves, connectors, filter housings, scissors, nozzles, flower pots, flower stands, etc.; the medical technology equipment includes, but is not limited to, disposable syringes, sterilizers, medicine bottles, surgical instruments, dialysis components, sterile containers, etc.; the motor vehicle components include, but are not limited to, engine compartment components (such as ignition coil housings, sensor housings, water pump impellers, cooling system components), automotive electronics (such as connectors, ECU housings, wiring harness connectors, radar covers, battery management system components), interior and exterior trim (such as dashboards, door panels, interior support brackets, seat frames), functional components (such as fan blades, rearview mirror brackets, door lock components, sunroof components, etc.).

[0086] Fifthly, the present invention provides the application of syndiotactic polystyrene prepared by the preparation method described in the first aspect, or syndiotactic polystyrene as described in the second aspect, or resin compositions as described in the third aspect, in the preparation of household goods, electronic components, household appliances, gardening equipment, medical technology equipment, and motor vehicle parts.

[0087] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0088] Compared with the prior art, the beneficial effects of the present invention are as follows: The method for preparing syndiotactic polystyrene provided by this invention involves adding a saturated hydrocarbon mixture during the polymerization stage and controlling the content of the saturated hydrocarbon mixture within a specific range. This method is beneficial for improving the color uniformity of the product and, when blended with additives, for improving the dispersion uniformity of the additives, thereby obtaining a product with superior performance. Furthermore, it has virtually no impact on the mechanical properties and processing performance of the material (it will not lead to an increase in mold fouling during subsequent processing). Detailed Implementation

[0089] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0090] In this invention, the content of the saturated hydrocarbon mixture is based on the mass of the added raw materials. That is, if the amount of saturated hydrocarbon mixture added is m1 and the amount of styrene monomer added is m2, then the mass percentage of the saturated hydrocarbon mixture in the syndiotactic polystyrene is = m1 / (m1+m2)×100%.

[0091] In this invention, the method for testing the kinematic viscosity ν of the saturated hydrocarbon mixture includes: determination according to GB / T 265-1988 "Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity of Petroleum Products", specifically including the following steps: First, sample pretreatment is performed by filtering the saturated hydrocarbon mixture to be tested through a 0.45μm organic microporous membrane, and selecting a Canon-Fensk capillary viscometer of appropriate specifications according to the estimated viscosity range, wherein the range is 4.5-6.0mm. 2 The viscosity range is selected using a 0.8-1.0 mm inner diameter viscometer, and 6.1-16.5 mm... 2 / s Use a viscometer with an inner diameter of 1.2-1.5mm, or 16.6-28.0mm. 2 A 2.0-3.0 mm inner diameter viscometer is selected. During testing, the viscometer with the sample loaded is placed vertically in a constant temperature water bath at 40±0.05℃ and maintained at this temperature for 10±0.5 minutes. The precise time t for the sample to flow through the upper and lower marks of the viscometer is measured. The kinematic viscosity is calculated using the formula ν=C·t, where C is the viscometer calibration constant. The measurement is repeated three times, and the deviation of each measurement result from the average value should not exceed 0.35%. The final arithmetic mean is taken as the measurement result, accurate to 0.01 mm. 2 / s.

[0092] In this invention, all materials used can be purchased commercially or prepared using conventional methods. Unless otherwise specified, the materials used in this invention are as follows.

[0093] All white oils used in this invention are industrial-grade white oils, purchased from Suzhou Sepahan Special Oils Co., Ltd.

[0094] White oil-1:10#, kinematic viscosity 10.0 mm 2 / s (40℃).

[0095] White oil-2: 7#, kinematic viscosity 6.8 mm. 2 / s (40℃).

[0096] White oil-3: 15#, kinematic viscosity 15mm 2 / s (40℃).

[0097] Polydimethylsiloxane: purchased from Beijing Huawirui Chemical Technology Co., Ltd., with a dynamic viscosity of 350 mPa·s (25℃).

[0098] Example 1 This embodiment provides a method for preparing syndiotactic polystyrene, wherein the method for preparing syndiotactic polystyrene employs a batch polymerization method and specifically includes the following steps.

[0099] A 20L vertical reactor with a double-ribbed agitator was heated to 100℃, vacuum dried for 2 hours, and purged three times with high-purity nitrogen, finally replacing it with a nitrogen-hydrogen mixture with a hydrogen integral of 10%. After the reactor temperature dropped to 70℃, 10.8 kg of styrene (12L) and 200 g of white oil-1 were added to the reactor. According to the formula, the prepared catalyst was added: 100 mL of toluene solution containing 200 mmol of methylaluminoxane, 100 mL of toluene solution containing 200 mmol of triisobutylaluminum, and 1 mmol of pentamethylcyclopentadienyltrimethoxytitanium (…). The resulting catalyst solution was fed into the reactor, with a concentration of pentamethylcyclopentadienyltrimethoxytitanium relative to styrene of 8 × 10⁻⁶. -5 The reaction was carried out at mol / L for 2 hours, during which no sudden increase in internal temperature or stirring torque occurred. After the reaction, the reactor temperature was gradually increased to 120℃ at a rate of 1℃ / min, and the vacuum was increased to -0.1MPa at a rate of 2KPa / min for devolatilization. No sudden increase in stirring torque occurred during the devolatilization process. After devolatilization, the ball valve located in the reactor outlet pipe was opened to discharge the material. The process was smooth, and sPS powder was obtained, which is the syndiotactic polystyrene.

[0100] Examples 2-9 and Comparative Examples 1-5 each provide a method for preparing syndiotactic polystyrene. Unless otherwise specified, the methods for preparing syndiotactic polystyrene provided in Examples 2-9 and Comparative Examples 1-5 are the same as those in Example 1, with the only differences being the type and content of catalyst, the type and content of saturated hydrocarbon mixture, and process parameters; as shown in Tables 1-3.

[0101] The difference between the preparation method of syndiotactic polystyrene provided in Comparative Example 1 and Example 1 is that the white oil is added after polymerization is completed, that is, white oil-1 is not added during the polymerization stage. Then, the sPS powder obtained by polymerization is mixed evenly with the white oil to obtain the syndiotactic polystyrene. Other step parameters and raw material dosages are the same as in Example 1.

[0102] In the preparation method of syndiotactic polystyrene provided in Comparative Example 2, the stirring torque was too large during the devolatilization process, the motor alarmed and stopped, there was a large scraping sound when discharging, the discharge pipe was bridging during discharge, and agglomeration was found when disassembling.

[0103] Unless otherwise specified, the reaction pressure is 0.2 MPa.

[0104] It is pentamethylcyclopentadienyl titanium trichloride.

[0105] Table 1 Table 2 Table 3 Performance testing The syndiotactic polystyrene prepared in the examples and comparative examples was added to an extruder with antioxidant RIANOX 1098 for extrusion granulation, wherein the mass of antioxidant RIANOX 1098 was 0.2% of the mass of syndiotactic polystyrene, and the extrusion barrel temperature was 295°C; syndiotactic polystyrene particles were obtained; and the color uniformity of the obtained syndiotactic polystyrene particles was tested.

[0106] Color uniformity: The color of the sample was measured using a spectrophotometer (Color-Eye 7000A, X-rite). , , The value was determined, and a comprehensive color difference evaluation was performed according to ASTM D2244 standard, where the comprehensive color difference ΔE 00 Calculated according to the CIEDE2000 formula.

[0107] The resin composition was prepared by means of the syndiotactic polystyrene obtained in the examples and comparative examples. Specifically, the syndiotactic polystyrene particles were mixed with glass fiber GF-1 (ECS301HP-3-H), compatibilizer PPE-MAH, antioxidant RIANOX1098, and lubricant TR044W. The resin composition was then compounded and extruded using a twin-screw extruder to obtain granular products, which are the resin compositions. By weight, the syndiotactic polystyrene particles, glass fiber, compatibilizer, antioxidant, and lubricant were 67.5 parts, 30 parts, 2 parts, 0.2 parts, and 0.3 parts, respectively. The filler was fed separately from the side feed port. The extrusion temperature was 295°C. The mechanical properties of the resin composition and the mold fouling during processing were tested.

[0108] The preparation method of the compatibilizer maleic anhydride modified polyphenylene ether (PPE-MAH) includes: dry mixing 1 kg of the polyphenylene ether, 40 g of maleic anhydride and 0.1 g of dicumyl peroxide, and then performing melt extrusion granulation at 250°C to obtain the particulate compatibilizer of the maleic anhydride modified polyphenylene ether.

[0109] Mold fouling: The obtained resin composition was injection molded using an injection molding machine and a custom-made mold fouling collection mold at a barrel temperature of 320°C and a mold temperature of 40°C for 300 injection molding samples. Mold fouling was collected on the metal sheet at the vent. Mold fouling mass = total mass of metal sheet after 300 molding samples - initial mass of metal sheet.

[0110] Mechanical Properties: The obtained resin composition was injection molded using a barrel temperature of 295℃ and a mold temperature of 50℃ to produce dumbbell-shaped specimens (Type A specimens in ISO 527-2:2019, total length 170mm, tensile zone length 115mm, width 10mm, thickness 4mm) and strip specimens (length 80mm, width 10mm, thickness 4mm) for mechanical property testing. ① Tensile Strength: Tensile testing was performed using dumbbell-shaped specimens according to ISO 527-2:2019 standard; ② Flexural Modulus: Flexural testing was performed using strip specimens according to ISO 178:2019 standard.

[0111] The specific test results are shown in Table 4.

[0112] Table 4 As shown in Table 4, the method for preparing syndiotactic polystyrene provided by this invention, by adding a saturated hydrocarbon mixture during the polymerization stage and controlling the content of the saturated hydrocarbon mixture within the range of 0.5% to 5%, yields syndiotactic polystyrene particles with excellent color uniformity, good mechanical properties, and minimal mold fouling of the resin composition; the ΔE of the syndiotactic polystyrene... 00≤0.6, σ≤0.3, tensile strength≥40MPa, flexural modulus≥2848MPa, and the mass of fouling in the injection mold of the resin composition including the syndiotactic polystyrene is ≤1mg.

[0113] As can be seen from Examples 1, 8, and 9, the viscosity of the saturated hydrocarbon mixture is within a specific range, which is beneficial to further improve the color uniformity and mechanical properties of the particles, as well as to obtain less injection molding fouling.

[0114] As can be seen from the comparison between Example 1 and Comparative Example 1, the addition of saturated hydrocarbon mixture after polymerization results in poor color uniformity of the syndiotactic polystyrene particles.

[0115] As can be seen from Comparative Examples 2-5, when the amount of saturated hydrocarbon mixture added is not in the range of 0.5-5% or polydimethylsiloxane is used to replace the saturated hydrocarbon mixture, the color uniformity or mechanical properties of the obtained syndiotactic polystyrene particles are significantly reduced compared with the examples, and the scale accumulation is more serious.

[0116] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing syndiotactic polystyrene, characterized in that, The preparation method includes: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst and a mixture of saturated hydrocarbons to obtain the syndiotactic polystyrene; The mass percentage of the saturated hydrocarbon mixture in the syndiotactic polystyrene is 0.5% to 5%.

2. The preparation method according to claim 1, characterized in that, The mass percentage of the saturated hydrocarbon mixture in the syndiotactic polystyrene is 1% to 3%.

3. The preparation method according to claim 1, characterized in that, The saturated hydrocarbon mixture satisfies at least one of (1) to (2): (1) The saturated hydrocarbon mixture includes white oil; (2) The kinematic viscosity of the saturated hydrocarbon mixture at 40°C is 6.1~16.5 mm. 2 / s.

4. The preparation method according to claim 1, characterized in that, The catalyst comprises the following components: (A) Titanocene metal compounds; (B) Alkyl aluminum oxane b1, and / or compound b2 that can react with titanium metal compounds to form ionic complexes; (C) Organoaluminum compounds.

5. The preparation method according to claim 4, characterized in that, The catalyst satisfies at least one of (1) to (4): (1) The general formula of the component (A) is R 1 TiX 1 X 2 X 3 ; Among them, R 1 Selected from any one of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or fused polycyclic cyclopentadienyl containing at least one saturated ring; X 1 X 2 and X 3 Each of the substituents is independently selected from any one of hydrogen atoms, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkylsilyl, C6-C20 aryl, C6-C20 aryloxy, C6-C20 arylsilyl, C7-C20 aralkyl, and halogen atoms; the substituents include at least one of halogen atoms, C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 aryloxy, and C7-C20 aralkyl, and when the number of substituents is greater than 1, the substituents may be the same or different; (2) The alkylaluminoxane b1 is selected from C1~C8 straight-chain alkylaluminoxanes; (3) The general formula of compound b2 is: ; Among them, R 2 Selected from at least one of alkyl groups with ≥1 carbon atom and aryl groups with ≥6 carbon atom, R 2 Same or different; M is selected from at least one of B, Al, Si, P, and As; X 4 The group is selected from at least one of C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C7-C20 aralkyl, and C6-C20 haloaryl, where q is an integer from 2 to 8, and X 4 Same or different; (4) The general formula of the component (C) is R 3 p AlH 3-p ; Among them, R 3 Selected from C1~C8 alkyl groups, where 0≤p≤3 and p>1, R 3 Same or different.

6. The preparation method according to claim 4, characterized in that, The catalyst satisfies at least one of (1) to (4): (1) The molar ratio of aluminum to the titanoceramic metal compound in the alkylaluminoxane b1 is (10~1000):1; (2) The molar ratio of M to the titanium metal compound in compound b2 is (0.5~1.5):1; (3) The molar ratio of aluminum to titanium metal compound in component (C) is (10~1000):1; (4) The concentration of the titanium chromium compound relative to styrene is 1 × 10⁻⁶. -7 ~5×10 -4 mol / L.

7. The preparation method according to claim 1, characterized in that, The preparation method satisfies at least one of (1) to (5): (1) The reaction is carried out in a nitrogen-hydrogen mixture; (2) The reaction is carried out in a nitrogen-hydrogen mixture, wherein the volume fraction of hydrogen in the nitrogen-hydrogen mixture is 0.1% to 20%; (3) The reaction temperature is 0℃~100℃; (4) The pressure of the reaction is 0 MPa to 10 MPa; (5) The preparation method includes batch polymerization.

8. A syndiotactic polystyrene, characterized in that, The syndiotactic polystyrene is prepared using the preparation method described in any one of claims 1 to 7.

9. A resin composition, characterized in that, The resin composition comprises syndiotactic polystyrene and additives; the syndiotactic polystyrene is prepared by the preparation method according to any one of claims 1 to 7.

10. The resin composition according to claim 9, characterized in that, The resin composition satisfies at least one of (1) to (2): (1) The mass of the additive is 0.01 to 20 parts, based on 100 parts of the mass of the syndiotactic polystyrene; (2) The additives include at least one of antioxidants, crosslinking agents, crosslinking aids, lubricants, nucleating agents, plasticizers, flame retardants, colorants, antistatic agents, and compatibilizers.

11. An article characterized in that, The product is formed from syndiotactic polystyrene prepared by any one of the preparation methods described in claims 1 to 7, or syndiotactic polystyrene as described in claim 8, or the resin composition as described in claim 9 or 10.

12. The use of a syndiotactic polystyrene prepared by any one of claims 1 to 7, or a syndiotactic polystyrene as described in claim 8, or a resin composition as described in claim 9 or 10, in the preparation of household goods, electronic components, household appliances, gardening equipment, medical technology equipment, and motor vehicle parts.

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