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

Abstract

The application provides a syndiotactic polystyrene resin and a preparation method, a resin composition, an article and an application thereof, and belongs to the technical field of polymer materials. The syndiotactic polystyrene resin contains butanone-soluble substances; the mass percentage of the butanone-soluble substances in the syndiotactic polystyrene resin is less than 6%; and in the GPC spectrum of the butanone-soluble substances, the percentage of the response signal integral area corresponding to the component with a molecular weight greater than 10000 g / mol in the total integral area is 5% to 60%. In the application, the syndiotactic polystyrene resin has excellent heat resistance and low forming shrinkage.

Description

Technical Field

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

[0002] Syndiotactic polystyrene (sPS) is a high-performance crystalline polymer that combines lightweight, chemical resistance, and low water absorption, making it suitable for high-end applications such as electronics and automobiles. With the miniaturization of electronic products and the lightweighting of automobiles, there is a dual demand for sPS materials to possess both excellent heat resistance and low molding shrinkage to meet the stringent requirements of precision connectors and high-temperature structural components. Syndiotactic polystyrene is primarily prepared through the coordination polymerization of styrene catalyzed by metallocene catalysts. This catalyst system has a single active center characteristic, allowing for precise control of the stereoregular insertion of monomers, thereby obtaining polymers with high stereoregularity. However, in the industrial production of sPS, the formation of low molecular weight sPS oligomers and atactic polystyrene caused by chain transfer, active center deactivation, and coupling side reactions will affect the heat resistance of sPS. Syndiotactic polystyrene resins with excellent heat resistance typically exhibit higher molding shrinkage due to their high crystallinity.

[0003] Therefore, developing a syndiotactic polystyrene resin that combines excellent heat resistance and low molding shrinkage is an urgent problem to be solved in this field. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a syndiotactic polystyrene resin, its preparation method, resin composition, articles, and applications. The syndiotactic polystyrene resin exhibits both excellent heat resistance and low molding shrinkage.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a syndiotactic polystyrene resin, wherein the syndiotactic polystyrene resin contains butanone solubles; the mass percentage of butanone solubles in the syndiotactic polystyrene resin is <6%; and in the GPC spectrum of the butanone solubles, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10000 g / mol to the total integrated area is 5% to 60%.

[0007] In this invention, by controlling the mass percentage of methyl ethyl ketone (MEK) solubles in the syndiotactic polystyrene resin within the aforementioned range, and simultaneously controlling the proportion of MEK solubles with a molecular weight greater than 10,000 g / mol within a specific range, it is beneficial to improve the heat resistance of the syndiotactic polystyrene resin while also maintaining its low molding shrinkage. In the GPC spectrum of the MEK solubles, if the proportion of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10,000 g / mol to the total integrated area is less than 5%, the dimensional shrinkage of the syndiotactic polystyrene increases after molding; if it is greater than 60%, the heat resistance deteriorates; if the mass percentage of MEK solubles is greater than 6%, the heat resistance deteriorates.

[0008] In this invention, in the GPC spectrum of the butanone-soluble compound, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10000 g / mol to the total integrated area is 5% to 60%, for example, it can be 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or any of the above values, more preferably 10% to 50%.

[0009] In this invention, in the GPC spectrum of the butanone solubles, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight ≤10000g / mol accounts for 40%~95% of the total integrated area.

[0010] In this invention, the molecular weight distribution range of the butanone soluble substance is preferably 100 g / mol to 1,000,000 g / mol, and the molecular weight distribution coefficient of the butanone soluble substance is preferably 1 to 15.

[0011] In this invention, the weight-average molecular weight of the butanone soluble substance is preferably 2000 g / mol to 20000 g / mol.

[0012] In this invention, the mass percentage of butanone-soluble matter in the syndiotactic polystyrene resin is <6%, for example, it can be 0.1%, 0.2%, 0.4%, 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%, 5.2%, 5.4%, 5.6%, 5.8% or any of the above values, more preferably 1.4% to 5%.

[0013] In this invention, the methyl ethyl ketone solubles refer to substances that can be dissolved by methyl ethyl ketone under specific conditions, including but not limited to byproducts generated during the preparation of syndiotactic polystyrene. Specifically, the methyl ethyl ketone solubles include at least one of atactic polystyrene and low molecular weight syndiotactic polystyrene; the low molecular weight syndiotactic polystyrene is selected from syndiotactic polystyrene with a weight average molecular weight of 2000 g / mol to 20000 g / mol.

[0014] In this invention, the melt index of the syndiotactic polystyrene resin is preferably 3 g / 10 min to 31 g / 10 min.

[0015] In this invention, the melt index of the syndiotactic polystyrene resin was tested according to the ISO 1133-1:2022 standard method at 300°C and under a 1.2 kg load.

[0016] In this invention, the weight-average molecular weight of the syndiotactic polystyrene resin is more preferably 1.3 × 10⁻⁶. 5 g / mol ~ 2.6 × 10 5 g / mol.

[0017] In this invention, both the molecular weight and molecular weight distribution coefficient can be obtained by gel permeation chromatography.

[0018] In a second aspect, the present invention provides a method for preparing syndiotactic polystyrene according to the first aspect, the method comprising: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst, an inert solvent and a nitrogen-hydrogen mixture to obtain the syndiotactic polystyrene resin, wherein the catalyst comprises the following components.

[0019] (A) Titanocene metal compounds;

[0020] (B) Alkyl aluminum oxane;

[0021] (C) Compounds that can react with titanium metal compounds to form ionic complexes;

[0022] (D) Organoaluminum compounds;

[0023] (E) Pre-contact mixture of trialkylaluminum compound and alcohol compound.

[0024] In this invention, the inert solvent includes at least one of C3-C8 alkanes, C3-C8 cycloalkanes, and C6-C8 aromatics.

[0025] In this invention, the C3-C8 alkanes can be straight-chain alkanes or branched-chain alkanes, such as C4, C5, C6, and C7 alkanes, including but not limited to n-propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, isopropane, isobutane, neopentane, etc.

[0026] In this invention, the C3-C8 cycloalkanes can be C3-C8 cycloalkanes without substituents, or cycloalkanes with a total carbon number of 3-8 including substituents; for example, they can be C4, C5, C6, and C7 cycloalkanes, including but not limited to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, ethylcyclohexane, methylcyclobutane, etc.

[0027] In this invention, the C6-C8 aromatic hydrocarbons include toluene, ethylbenzene, etc.

[0028] Preferably, the inert solvent includes at least one of n-hexane, n-pentane, cyclopentane, or toluene.

[0029] In this invention, there are no particular restrictions on the contact order of the components in the catalyst.

[0030] In this invention, the contact temperature of each component in the catalyst is 0℃~100℃, and the contact occurs in an inert atmosphere such as nitrogen or argon.

[0031] Preferably, the general formula of component (A) is R 1 TiX 1 X 2 X 3 .

[0032] 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, halogen atom, C1~C12 alkyl, C1~C12 alkoxy, C1~C12 alkylsilyl, C6~C20 aryl, C6~C20 arylsilyl, C6~C20 aryloxy, and C7~C20 arylalkyl; the substituents include at least one of halogen atom, C1~C12 alkyl, C1~C12 alkoxy, C6~C20 aryl, C6~C20 aryloxy, and C7~C20 arylalkyl, and when the number of substituents is greater than 1, the substituents may be the same or different.

[0033] In this invention, the C1~C12 alkyl group can be, for example, C1, C2, C4, C6, C8, C10, or C11 alkyl; it can be a straight-chain alkyl group or a branched-chain alkyl group, and exemplary includes, but is 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.

[0034] In this invention, the C1~C12 alkoxy groups can be, for example, C1, C2, C4, C6, C8, C10, or C11 alkoxy groups; exemplary, including but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentoxy, n-hexoxy, and n-decoxy groups; the same expressions in the following text have the same meaning.

[0035] In this invention, C6 to C20 aryl groups can be, for example, C6, C8, C10, C12, C14, C16, or C18 aryl groups; exemplary, including but not limited to phenyl, biphenyl, naphthyl, phenanthryl, anthracene, etc.; the same expressions in the following text have the same meaning.

[0036] In this invention, the C6~C20 aryloxy group can be, for example, C6, C8, C10, C12, C14, C16, or C18 aryloxy groups; the aryloxy group refers to a group formed by replacing one H with an O in the aforementioned C6~C20 aryl groups; the same expression in the following text has the same meaning.

[0037] In this invention, C7-C20 aralkyl groups can be, for example, C8, C10, C12, C14, C16, or C18 aralkyl groups; the aralkyl group refers to a group formed by replacing at least one H in the aforementioned C6-C20 aryl groups with an alkyl group; the same expressions in the following text have the same meaning.

[0038] 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.

[0039] 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.

[0040] In this invention, the halogen atoms include F, Cl, Br, and I.

[0041] In this invention, the number of substituents in "substituted or unsubstituted" is ≥1. When the number of substituents is greater than 1, the substituents are the same or different.

[0042] 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.

[0043] Preferably, component (B) is selected from C1-C8 straight-chain alkylaluminoxanes.

[0044] In this invention, component (B) is the reaction product of C1~C8 straight-chain alkyl aluminum and water.

[0045] In this invention, component (B) includes at least one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, n-pentylaluminoxane, n-hexylaluminoxane, and n-heptylaluminoxane.

[0046] Preferably, the general formula of component (C) is: .

[0047] 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.

[0048] In this invention, component (C) includes at least one of triphenylmethyltetraphenylborate, triphenylmethyltetra(pentafluorophenyl)borate, tri(2,4,6-trimethylphenyl)methyltetra(pentafluorophenyl)borate, and triphenylmethyltetra(3,5-bistrifluoromethylphenyl)borate.

[0049] Preferably, the general formula of the component (D) is R.3 p AlH 3-p .

[0050] 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, n-butyl, n-pentyl, and n-hexyl; 0 ≤ p ≤ 3; when p > 1, R 3 Same or different.

[0051] In this invention, component (D) includes at least one of triisobutylaluminum, trimethylaluminum, triethylaluminum, triisopropylaluminum, diisobutylaluminum hydride, tri-n-butylaluminum, tri-n-hexylaluminum, di-n-butylaluminum, diisopropylaluminum, and n-butylaluminum.

[0052] Preferably, the trialkylaluminum compound in component (E) has the general formula R. 4 3Al.

[0053] Among them, R 4 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, n-butyl, isobutyl, n-pentyl, and n-hexyl; R 4 Same or different.

[0054] Preferably, the alcohol compound in component (E) is selected from at least one of C1-C16 straight-chain alcohols, C3-C16 branched-chain alcohols, cycloalkanols with ≥3 carbon atoms, and aromatic alcohols with ≥6 carbon atoms.

[0055] In this invention, C1 to C16 straight-chain alcohols can be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C10, C12, C14, and C16 straight-chain alcohols, including but not limited to methanol, ethanol, n-propanol, n-butanol, n-hexanol, n-decanol, n-dodecanol, and n-tetradecanol.

[0056] In this invention, the C3~C16 branched alcohols can be, for example, C3, C4, C5, C6, C7, C8, C10, C12, C14, or C16 branched alcohols, including but not limited to isopropanol, tert-butanol, isobutanol, 2-hexanol, isohepanol, isooctanol, and isothietol.

[0057] In this invention, cycloalkanols with ≥3 carbon atoms can have a carbon number of 3, 4, 5, 6, 7, 8, 9, 10, 12, 14 or any range of the above values; exemplary examples include but are not limited to cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, etc.

[0058] In this invention, aromatic alcohols with ≥6 carbon atoms may have a carbon number of 6, 8, 10, 12, 14, 16, 18, 20 or any range of the above values; exemplary examples include but are not limited to benzyl alcohol, phenylethanol, diphenylethanol, triphenylethanol, o-methylbenzyl alcohol, biphenyl-4-methanol, 1-naphthylethanol, etc.

[0059] In this invention, the pre-contact mixture of the trialkylaluminum compound and the alcohol compound includes dialkylaluminum alkoxide, alkylaluminum diol, and aluminum triol, with the dialkylaluminum alkoxide being the main component.

[0060] Preferably, the molar ratio of aluminum to titanium metal compound in component (B) is (10~1000):1, wherein the specific value of (10~1000) can be, for example, 20, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000 or any range between the above values.

[0061] Preferably, the molar ratio of M to the titanoceramic metal compound in component (C) 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.

[0062] Preferably, the molar ratio of aluminum to titanium metal compound in component (D) is (10~1000):1, wherein the specific value of (10~1000) can be, for example, 20, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000 or any range between the above values.

[0063] Preferably, the molar ratio of aluminum to titanium metal compound in component (E) is (9~1000):1, wherein the specific value of (9~1000) can be, for example, 10, 20, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000 or any range between the above values.

[0064] Preferably, in component (E), the molar ratio of aluminum in the trialkylaluminum compound to hydroxyl groups in the alcohol compound is 1:(0.05~1), wherein the specific value of (0.05~1) can be, for example, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or any range between the above values.

[0065] Preferably, the component (E), the trialkylaluminum compound, is pre-contacted with the alcohol compound in the presence of a solvent.

[0066] Preferably, the solvent includes toluene.

[0067] Preferably, the concentration of component (A) relative to styrene is 1 × 10⁻⁶. -7 mol / L ~ 5×10 -4 mol / L, for example, 2×10 -7 mol / L, 4×10 -7 mol / L, 6×10 -7 mol / L, 8×10 -7 mol / L, 1×10 -6 mol / L, 2×10 -6 mol / L, 4×10 -6 mol / L, 6×10 -6 mol / L, 8×10 -6 mol / L, 1×10 -5 mol / L, 2×10 -5 mol / L, 4×10 -5 mol / L, 6×10 -5 mol / L, 8×10 -5 mol / L, 1×10 -4 mol / L, 2×10 -4 mol / L, 4×10 -4 The range of mol / L or any of the above values ​​is more preferably 5 × 10⁻⁶. -6 mol / L ~ 2×10 -4 mol / L, more preferably 1×10-5 mol / L ~ 1×10 -4 mol / L.

[0068] In this invention, the volume fraction of hydrogen in the nitrogen-hydrogen mixture is 0.1% to 15%, 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% or any range between the above values.

[0069] Preferably, the temperature of the addition polymerization reaction 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 range of the above values.

[0070] Preferably, the pressure of the addition polymerization reaction 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.

[0071] In this invention, the pressure is measured using an apparent pressure gauge.

[0072] Preferably, the preparation method includes: continuously feeding styrene and a catalyst into a reactor in the presence of a nitrogen-hydrogen mixture, while simultaneously feeding an inert solvent into the reactor to carry out an addition polymerization reaction.

[0073] In this invention, the reactor is pre-filled with powder particles and is in a fluidized state; the powder is syndiotactic polystyrene resin powder (sPS powder), used to maintain the solid-phase dispersion state and ensure the phase stability of the system; the sPS powder is a fine powder with a particle size (D50) of 50μm-500μm, which is dried to constant weight and then placed in the reactor; this invention has no special requirements for syndiotactic polystyrene (sPS) powder, and commercially available products or laboratory-made samples are applicable.

[0074] In this invention, the particle size of the sPS powder is tested using a woven wire sieve according to ISO 3310-1:2016 standard.

[0075] In this invention, the content of methyl ethyl ketone (MEK) solubles in syndiotactic polystyrene resin can be controlled by adjusting the composition of the catalyst (including the types and ratios of each component), the volume fraction of hydrogen in the nitrogen-hydrogen mixture, and the type of inert solvent. This also controls the proportion of the integral area of ​​the response signal corresponding to the component with a molecular weight greater than 10,000 g / mol in the GPC spectrum of the MEK solubles to the total integral area.

[0076] In this invention, the preparation method of the syndiotactic polystyrene resin is not limited to the above-mentioned method, and any method that can obtain the specific syndiotactic polystyrene resin of this invention is acceptable; for example, the syndiotactic polystyrene resin of this invention can also be obtained by mixing syndiotactic polystyrene resins with different methyl ethyl ketone (MEK) soluble contents and different MEK soluble compositions (i.e., in the GPC spectrum of MEK solubles, the percentage of the response signal integral area corresponding to the component with a molecular weight greater than 10000 g / mol to the total integral area).

[0077] Thirdly, the present invention provides a resin composition comprising the syndiotactic polystyrene resin described in the first aspect, and further comprising at least one of fillers, compatibilizers, and other additives.

[0078] Preferably, the resin composition contains ≥50% by mass of meso-regulated polystyrene resin, for example, 55%, 60%, 70%, 80%, 90%, 98% or any of the above values.

[0079] Preferably, by weight, the resin composition comprises 50-100 parts of syndiotactic polystyrene resin (e.g., 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or any range between the above values), and 0.5-50 parts of filler (e.g., 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, 3...). 2 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts or any of the above values), 0.1 to 10 parts of compatibilizer (e.g., 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts or any of the above values), and 0 to 20 parts of other adjuvants (e.g., 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or any of the above values).

[0080] Preferably, the filler includes at least one of fibrous filler, granular filler, and powdered filler.

[0081] Preferably, the fibrous filler includes at least one of glass fiber, carbon fiber, whiskers, ceramic fiber, and metal fiber.

[0082] Preferably, the granular filler and the 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.

[0083] 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.

[0084] Preferably, 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.

[0085] Preferably, the compatibilizer comprises modified styrene-based polymers and / or modified polyphenylene ether-based polymers.

[0086] Preferably, the modified styrene-based polymer includes 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 ionomer, 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.

[0087] Preferably, the modified polyphenylene ether polymer includes at least one of 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.

[0088] Preferably, 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).

[0089] 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.

[0090] Preferably, the other additives include at least one of rubbery elastomers, antioxidants, lubricants, crosslinking agents, crosslinking aids, nucleating agents, plasticizers, flame retardants, colorants, and antistatic agents.

[0091] In this invention, the rubber-like elastomer includes, but is not limited to, at least one of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS).

[0092] 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.

[0093] In this invention, the lubricant includes, but is not limited to, at least one of ethylene bis-stearamide (EBS), glyceryl monostearate, oleamide, and erucamide.

[0094] In this invention, the crosslinking agent includes, but is not limited to, dicumyl peroxide, benzoyl peroxide, divinylbenzene, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, etc.

[0095] In this invention, the crosslinking aids include, but are not limited to, triallyl isocyanurate, trimethylolpropane trimethacrylate, etc.

[0096] 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.

[0097] In this invention, the plasticizers include, but are not limited to, dioctyl phthalate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate, and epoxidized soybean oil.

[0098] In this invention, the flame retardants include, but are 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.

[0099] In this invention, the antistatic agent includes, but is not limited to, quaternary ammonium salt antistatic agents, fatty acid ester antistatic agents, etc.

[0100] In this invention, the method for preparing the resin composition includes: mixing syndiotactic polystyrene resin and optionally fillers, compatibilizers, and other additives, and extruding to obtain the resin composition.

[0101] Fourthly, the present invention provides an article comprising the syndiotactic polystyrene resin described in the first aspect or the resin composition described in the third aspect.

[0102] 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.).

[0103] Fifthly, the present invention provides the use of syndiotactic polystyrene resin as described in the first aspect or resin composition 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.

[0104] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0105] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0106] The syndiotactic polystyrene resin provided by this invention contains butanone solubles, and by controlling the content of butanone solubles and the proportion of components with a molecular weight greater than 10,000 g / mol within a specific range, syndiotactic polystyrene can possess both excellent heat resistance and low molding shrinkage, while ensuring its cost competitiveness. Detailed Implementation

[0107] 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.

[0108] In this invention, the method for testing the content of methyl ethyl ketone (MEK) solubles includes: crushing the test sample (i.e., syndiotactic polystyrene particles) into powder (35 mesh) using a solid pulverizer (Changzhou Surui Instrument Co., Ltd., XA-3), and then drying it to constant weight. Take 5.0000±0.0100g of the dried powder, weigh it and record the weight as m1, and wrap it tightly with type 102 qualitative filter paper as specified in GB / T1914-2017 to prepare the test sample. Place three of the above test samples in a Soxhlet extractor with an effective working volume of 250mL and a bottom flask volume of 1000mL. Use 650mL of once-distilled MEK as solvent, and continuously reflux the solvent at its boiling point for 10h, with 3±0.5 complete extraction cycles per hour. After extraction, the sample was removed and thoroughly washed three times with ethanol. It was then placed in a vacuum drying oven, and the vacuum was slowly drawn to -0.1 MPa, followed by gradual heating to 150°C. The drying oven was equipped with a cold trap containing liquid nitrogen, which was replaced periodically. The sample mass after constant weight was deducted from the filter paper mass and recorded as m2. The content of methyl ethyl ketone solubles = (m... 1- m2) / m1×100%.

[0109] In this invention, in the GPC spectrum of the butanone-soluble compound, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10000 g / mol relative to the total integrated area (denoted as M) is defined as follows: ＞10000 The analysis was performed using an Agilent 1260 gel permeation chromatography system. The chromatographic columns consisted of three columns connected in series: PLgel 5μm Mixed-c (300mm × 7.5mm), PLgel 10μm Mixed-b (300mm × 7.5mm), and PLgel 5μm Guard (50mm × 7.5mm). Molecular weight was determined using a differential refractive index (RI) detector, calculated according to the standard calibration curve for polystyrene standards. The molecular weights mentioned are the apparent molecular weights measured by GPC, and the standard molecular weight calibration range is 580–6,570,000. Molecular weights below 580 are extrapolated values ​​calculated based on the calibration curve extension. Tetrahydrofuran was used as the mobile phase at a flow rate of 1 mL / min and a column temperature of 35 °C. The sample was dissolved in tetrahydrofuran (2 mg / mL) and injected in 20 μL. Data were processed using Agilent GPC software, and the percentage of the integral area corresponding to the component with a molecular weight higher than 10000 g / mol was calculated based on direct integration of the measured GPC curves. The molecular weight distribution data obtained under the same test conditions and calibration system are comparable.

[0110] Example 1

[0111] This embodiment provides a syndiotactic polystyrene resin, wherein the mass percentage of butanone-soluble matter in the syndiotactic polystyrene resin is 3.5%, M ＞10000 It is 30%.

[0112] The preparation method of the syndiotactic polystyrene resin includes: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst, n-hexane, and a nitrogen-hydrogen mixture with a hydrogen gas fraction of 1% to obtain the syndiotactic polystyrene.

[0113] The catalyst comprises the following components.

[0114] (A) Pentamethylcyclopentadienyl titanium trichloride.

[0115] (B) Methylaluminoxane.

[0116] (C) Triphenylmethyl-tetra(pentafluorophenyl)borate.

[0117] (D) Triisobutylaluminum.

[0118] (E) Pre-contact mixture of triisobutylaluminum and triphenylmethanol.

[0119] The amount of component (A) relative to styrene is 5 × 10⁻⁶. -5 mol / L. The molar ratio of aluminum in component (B) to that in component (A) is 50:1; the molar ratio of boron in component (C) to that in component (A) is 1:1; the molar ratio of aluminum in component (D) to that in component (A) is 100:1. The molar ratio of aluminum in triisobutylaluminum in component (E) to that in component (A) is 10:1.

[0120] Toluene was used as the solvent for preparing the catalyst. Triisobutylaluminum, triphenylmethyl-tetra(pentafluorophenyl)borate, and methylaluminoxane were each mixed with toluene to prepare 10%, 1%, and 10% (w / w) toluene solutions of triisobutylaluminum, triphenylmethyl-tetra(pentafluorophenyl)borate, and methylaluminoxane, respectively. Triphenylmethanol was prepared as a 5% toluene solution and then mixed with the triisobutylaluminum to triphenylmethanol solution at a molar ratio of 1:0.8 at room temperature for 10 minutes to obtain a pre-contact mixture of triisobutylaluminum and triphenylmethanol. Then, the toluene solutions of triisobutylaluminum, pentamethylcyclopentadienyl titanium trichloride, triphenylmethyl-tetra(pentafluorophenyl)borate, methylaluminoxane, and the pre-contact mixture of triisobutylaluminum and triphenylmethanol were mixed according to the formulated amounts to obtain the mixed catalyst.

[0121] The specific method includes: heating a 1000L vertical reactor with a double-ribbed agitator to 100℃, vacuum drying for 2 hours, purging with high-purity nitrogen three times, and finally purging with a nitrogen-hydrogen mixture with a hydrogen integral of 1%, maintaining a slight positive pressure (50KPa) inside the reactor. Once the reactor temperature drops to 70℃, 250kg of pre-treated SPS powder (D50 of 300μm) is added to the reactor and dried under nitrogen flow for 2 hours. Then, according to the formulation, the mixed catalyst and styrene are continuously added to the reactor at a styrene flow rate of 100L / h, while simultaneously supplying hexane to the reactor. By controlling the reactor pressure and condensate return flow, the internal temperature is maintained at 70±1℃. After continuous operation for 2 hours, the bottom discharge valve of the reactor is opened and opened every 20 minutes to obtain the syndiotactic polystyrene resin.

[0122] Examples 2-9 and Comparative Examples 1-5 each provide a syndiotactic polystyrene resin, with a mass percentage of butanone-soluble matter and M... ＞10000 The specific process parameters are shown in Table 1-2. Unless otherwise specified, the preparation methods are the same as those in Example 1, with the only differences being the type of catalyst, the ratio, and the reaction conditions.

[0123] Table 1

[0124]

[0125] Example 10

[0126] This embodiment provides a syndiotactic polystyrene resin. The preparation method of the syndiotactic polystyrene resin includes: taking 50 parts of syndiotactic polystyrene resin from Comparative Example 1 and 50 parts of syndiotactic polystyrene resin from Comparative Example 2, and mixing them thoroughly and uniformly to obtain the syndiotactic polystyrene resin; the mass content of butanone-soluble matter in the syndiotactic polystyrene is 4.8%, M ＞10000 It is 44%.

[0127] Table 2

[0128]

[0129] In this invention, the materials used in the application examples and comparative application examples can be purchased commercially or prepared using conventional methods; unless otherwise specified, the materials used in this invention are as follows.

[0130] Polyphenylene oxide (PPE): LXR035.

[0131] Maleic anhydride modified polyphenylene ether (PPE-MAH): 1 kg of the polyphenylene ether, 40 g of maleic anhydride and 0.1 g of dicumyl peroxide are dry-mixed and then melt-extruded and granulated at 250 °C to obtain the particulate compatibilizer of the maleic anhydride modified polyphenylene ether.

[0132] Fumaric acid modified polyphenylene ether (PPE-FA): 1 kg of the polyphenylene ether, 40 g of fumaric acid and 0.1 g of dicumyl peroxide are dry mixed and then melt-extruded and granulated at 250 °C to obtain the particulate compatibilizer of the fumaric acid modified polyphenylene ether.

[0133] Glass fiber (GF-1): ECS301HP-3-H.

[0134] Application Examples 1-14, Comparative Application Examples 1-5

[0135] Application Examples 1-14 and Comparative Application Examples 1-5 each provide a resin composition, the formulation of which, by weight, is shown in Tables 3 and 4; wherein, " / " indicates that the component is not in the formulation; the preparation method of the resin composition includes: mixing the components, then using a twin-screw extruder to knead the resin composition, extruding to obtain a granular product, that is, obtaining the resin composition; wherein the filler needs to be fed separately from the side feed port; the extrusion temperature is 295°C.

[0136] Table 3

[0137]

[0138] Table 4

[0139]

[0140] Performance testing

[0141] (1) Heat distortion temperature (HDT): The resin compositions provided in the application example and the comparative application example were used to make 80mm×10mm×4mm strips using an injection molding machine with a barrel temperature of 295°C and a mold temperature of 50°C. The strips were annealed at 180°C for 2 hours before testing. During the test, the silicone oil bath heating rate was 2°C / min. The HDT value was the temperature recorded when the bending strain of the strip reached 0.2% under a load of 1.8MPa.

[0142] (2) Dimensional shrinkage: Determined according to the ISO 294-1 standard method, the resin compositions provided in the application examples and comparative application examples were used in an injection molding machine with a barrel temperature of 295°C and a mold temperature of 50°C to prepare strip samples conforming to standard dimensions (75mm×30mm×2.5mm) using a standard mold. The sample size L was accurately measured using a two-dimensional image analyzer and compared with the mold cavity size L0. The dimensional shrinkage value was calculated according to the formula [(L0 - L) / L0]×100%, which is the molding shrinkage rate.

[0143] The specific test results are shown in Table 5.

[0144] Table 5

[0145]

[0146] As shown in Table 5, the syndiotactic polystyrene resin provided by the present invention controls the content of methyl ethyl ketone (MEK) solubles in the syndiotactic polystyrene resin to be less than 6%, and the proportion of MEK solubles with a molecular weight greater than 10000 g / mol is in the range of 5% to 60%, which enables the syndiotactic polystyrene resin to have both excellent heat resistance and low molding shrinkage. The heat distortion temperature of the material including the syndiotactic polystyrene resin is ≥235℃, the longitudinal dimensional shrinkage is ≤0.19%, and the transverse dimensional shrinkage is ≤0.55%.

[0147] As can be seen from Application Example 9 and Comparative Application Example 1, the proportion of components with a molecular weight greater than 10000 g / mol in the methyl ethyl ketone solubles is close, and the content of the methyl ethyl ketone solubles is greater than 6%, resulting in a significant reduction in its heat distortion temperature.

[0148] As can be seen from Application Example 10 and Comparative Application Example 2, the content of methyl ethyl ketone soluble matter is similar. When the proportion of the component with a molecular weight greater than 10000 g / mol in the methyl ethyl ketone soluble matter is less than 5%, its dimensional shrinkage rate is relatively high.

[0149] As can be seen from Application Examples 1 and 2 and Comparative Application Examples 3, 4 and 5, the content of soluble matter in methyl ethyl ketone is similar. When the proportion of components with a molecular weight greater than 10,000 g / mol in the soluble matter of methyl ethyl ketone is greater than 60%, its heat distortion temperature is significantly reduced.

[0150] 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 syndiotactic polystyrene resin, characterized in that, The syndiotactic polystyrene resin contains methyl ethyl ketone (MEK) solubles; the mass percentage of MEK solubles in the syndiotactic polystyrene resin is <6%. In the GPC spectrum of the butanone solubles, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10000 g / mol is 5% to 60% of the total integrated area.

2. The syndiotactic polystyrene resin according to claim 1, characterized in that, In the GPC spectrum of the butanone solubles, the percentage of the integrated area of ​​the response signal corresponding to the component with a molecular weight greater than 10000 g / mol is 10% to 50% of the total integrated area.

3. The syndiotactic polystyrene resin according to claim 1, characterized in that, The mass percentage of butanone-soluble matter in the syndiotactic polystyrene resin is 1.4% to 5%.

4. A method for preparing syndiotactic polystyrene resin according to any one of claims 1 to 3, characterized in that, The preparation method includes: subjecting styrene monomer to an addition polymerization reaction in the presence of a catalyst, an inert solvent, and a nitrogen-hydrogen mixture to obtain the syndiotactic polystyrene resin, wherein the catalyst comprises the following components: (A) Titanocene metal compounds; (B) Alkyl aluminum oxane; (C) Compounds that can react with titanium metal compounds to form ionic complexes; (D) Organoaluminum compounds; the general formula of component (D) 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; (E) Pre-contact mixture of trialkylaluminum compounds and alcohol compounds; The inert solvent includes at least one of C3-C8 alkanes, C3-C8 cycloalkanes, and C6-C8 aromatics; The general formula of component (C) 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; The molar ratio of M to component (A) in component (C) is (0.5~1.5):1; The molar ratio of aluminum to titanium metal compound in component (B) is (10~1000):1; The molar ratio of aluminum to titanium metal compound in component (D) is (10~1000):1; The molar ratio of aluminum to the titanium metal compound in component (E) is (9~1000):

1.

5. The preparation method according to claim 4, characterized in that, The catalyst satisfies at least one of (1) to (5): (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 atom, halogen atom, C1-C12 alkyl, C1-C12 alkylsilyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 arylsilyl, C6-C20 aryloxy, and C7-C20 arylalkyl; the substituents include at least one of halogen atom, C1-C12 alkyl, C1-C12 alkoxy, C6-C20 aryl, C6-C20 aryloxy, and C7-C20 arylalkyl, and when the number of substituents is greater than 1, the substituents may be the same or different; (2) The component (B) is selected from C1~C8 straight-chain alkylaluminoxanes; (3) The general formula of the trialkylaluminum compound in component (E) is R 4 3Al; Among them, R 4 Selected from C1~C8 alkyl groups, R 4 Same or different; (4) The alcohol compound in component (E) is selected from at least one of C1~C16 straight-chain alcohols, C3~C16 branched-chain alcohols, cycloalkanols with ≥3 carbon atoms, and aromatic alcohols with ≥6 carbon atoms; (5) The component (E), the trialkylaluminum compound and the alcohol compound are pre-contacted in the presence of a solvent, the solvent including toluene.

6. The preparation method according to claim 4, characterized in that, The catalyst satisfies at least one of (1) to (2): (1) In the component (E), the molar ratio of aluminum in the trialkylaluminum compound to hydroxyl groups in the alcohol compound is 1:(0.05~1); (2) The concentration of component (A) relative to styrene is 1 × 10⁻⁶. -7 mol / L ~ 5×10 -4 mol / L.

7. The preparation method according to claim 4, characterized in that, The preparation method satisfies at least one of (1) to (5): (1) The inert solvent includes at least one of n-hexane, n-pentane, cyclopentane or toluene; (2) The volume fraction of hydrogen in the nitrogen-hydrogen mixture is 0.1% to 15%; (3) The temperature of the addition polymerization reaction is 0℃~100℃; (4) The pressure of the addition polymerization reaction is 0 MPa to 10 MPa; (5) The preparation method includes: continuously feeding styrene and catalyst into a reactor in the presence of a nitrogen-hydrogen mixture, while simultaneously feeding an inert solvent into the reactor to carry out an addition polymerization reaction.

8. A resin composition, characterized in that, The resin composition comprises the syndiotactic polystyrene resin as described in any one of claims 1 to 3, and further comprises at least one of fillers, compatibilizers, and other additives.

9. The resin composition according to claim 8, characterized in that, The resin composition comprises, by weight, 50-100 parts of syndiotactic polystyrene resin, 0.5-50 parts of filler, 0.1-10 parts of compatibilizer, and 0-20 parts of other additives.

10. The resin composition according to claim 9, characterized in that, The resin composition satisfies at least one of (1) to (3): (1) The packing material includes at least one of fibrous packing material, granular packing material, and powdered packing material; (2) The compatibilizer includes modified styrene polymers and / or modified polyphenylene ether polymers; (3) The other additives include at least one of rubber elastomers, antioxidants, lubricants, crosslinking agents, crosslinking aids, nucleating agents, plasticizers, flame retardants, colorants, and antistatic agents.

11. The resin composition according to claim 10, characterized in that, The resin composition satisfies at least one of (1) to (5): (1) The fibrous filler includes at least one of glass fiber, carbon fiber, whisker, ceramic fiber, and metal fiber; (2) 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; (3) The modified styrene 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 ionomer, 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; (4) The modified polyphenylene ether polymer includes at least one of 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. (5) 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-6-ethyl ... At least one of the following: 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-dipropyl-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).

12. The resin composition according to claim 11, characterized in that, The glass fiber has a length of 0.05mm to 50mm and a diameter of 5μm to 20μm.

13. An article characterized in that, The article comprises the syndiotactic polystyrene resin according to any one of claims 1 to 3 or the resin composition according to any one of claims 8 to 12.

14. The use of a syndiotactic polystyrene resin as described in any one of claims 1 to 3 or a resin composition as described in any one of claims 8 to 12 in the preparation of household goods, electronic components, household appliances, gardening equipment, medical technology equipment, and motor vehicle parts.

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