CN114891271A - Composite auxiliary agent and preparation method and application thereof - Google Patents

Composite auxiliary agent and preparation method and application thereof Download PDF

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Publication number
CN114891271A
CN114891271A CN202210734104.XA CN202210734104A CN114891271A CN 114891271 A CN114891271 A CN 114891271A CN 202210734104 A CN202210734104 A CN 202210734104A CN 114891271 A CN114891271 A CN 114891271A
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nucleating agent
antioxidant
light stabilizer
agent
ppm
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曹子卿
曹林
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Shandong Qirunyuan New Material Technology Co ltd
Shanghai Runji New Material Technology Co ltd
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Shandong Qirunyuan New Material Technology Co ltd
Shanghai Runji New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the technical field of plastic additives, in particular to a composite additive and a preparation method and application thereof. The composite auxiliary agent comprises an antioxidant, a light stabilizer, a modified nucleating agent and an acid absorbent; the raw materials of the modified nucleating agent comprise the nucleating agent and the modifying agent; the mass ratio of the nucleating agent to the modifying agent is 1.5-10: 1. the composite additive prepared by the invention is applied to polyolefin, is irradiated under the absorbed dose of 20, 30, 40 and 50kGy, has excellent performance indexes, and solves the problem of irradiation degradation of medical PP materials.

Description

Composite auxiliary agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of plastic additives, in particular to a composite additive and a preparation method and application thereof.
Background
At present, the sterilization methods of medical materials mainly comprise two methods: one is ethylene oxide sterilization and the other is irradiation sterilization. Ethylene Oxide (EO) sterilization is a chemical sterilization using EO as a sterilant, where EO can chemically react with groups on proteins, alkylating the hydroxyl groups, deactivating microbial proteins and causing microbial death. The radiation sterilization is to utilize the nuclear radiation principle to cause the death of microorganisms by utilizing the energy of atomic energy rays, thereby achieving the purpose of sterilization. Radiation sterilization is most commercially performed using gamma rays generated by cobalt-60 and electron beams generated by an electron accelerator.
The traditional ethylene oxide disinfection method has the defects of air pollution and harmful residues on medical instruments to human bodies, needs to be kept still for 7 days for analysis after disinfection, and can be packaged and delivered after the EO residual quantity is lower than a required value.
Polypropylene is widely used in the field of medical devices due to its excellent overall properties. However, the radiation stability of ordinary medical PP is poor, the physical and mechanical properties of PP after radiation sterilization are deteriorated, the color of PP becomes yellow, and the aging phenomenon becomes more serious with the increase of storage time, especially under high temperature and high humidity, so that it is impossible to use PP. The problems of mechanical property reduction and yellowing caused by irradiation degradation severely limit the application of PP materials in the fields of medical instruments and other irradiation processing, so that the solution of the irradiation degradation of PP has great practical application value.
PP is more seriously degraded after being irradiated, sterilized and stored for a period of time, and the phenomenon is called as post-irradiation effect. Currently, the explanation for the "post-irradiation effect" is: after the PP is irradiated by gamma rays, generated free radicals are trapped in a crystal region of the PP, the service life of the trapped free radicals is long, and during storage, the free radicals migrate from the crystal region to an interface between the crystal region and an amorphous region and then undergo an oxidation reaction with oxygen in the air, so that a 'post-irradiation effect' is generated.
Similar to the degradation and aging mechanism of polymer materials, the inhibition of the irradiation coloring phenomenon requires the inhibition of the generation of macromolecular free radicals and the secondary reaction thereof, so that the free radicals generated in the irradiation process are converted into stable structures. However, the problem of polymer irradiation induced color is not much studied at present, and is generally considered to be caused by two factors: (1) the conjugated structure generated in the polymer, namely the isomerization of the macromolecular free radical structure forms double bonds and conjugated double bonds, and the conjugated structure absorbs partial natural light to cause color; (2) the free radicals existing in the crystal region of the polymer have long life due to the collapse of the free radicals, and react to form a chromogenic group after contacting with oxygen in the air to cause color.
In conclusion, the development of a novel radiation-resistant composite assistant applied to polyolefin becomes one of the problems to be solved in the field.
Disclosure of Invention
The first purpose of the invention is to provide a composite auxiliary agent, which comprises an antioxidant, a light stabilizer, a modified nucleating agent and an acid acceptor; the raw materials of the modified nucleating agent comprise the nucleating agent and the modifying agent; the mass ratio of the nucleating agent to the modifying agent is 1.5-10: 1.
preferably, the mass ratio of the nucleating agent to the modifying agent is 4-7: 1.
more preferably, the mass ratio of the nucleating agent to the modifying agent is 5: 1.
in one embodiment, the composite auxiliary agent comprises 1000-2000 ppm of antioxidant, 800-2000 ppm of light stabilizer, 1000-10000 ppm of modified nucleating agent and 200-700 ppm of acid acceptor according to mass concentration.
Preferably, the composite auxiliary agent comprises 1000-2000 ppm of antioxidant, 1000-2000 ppm of light stabilizer, 1000-5000 ppm of modified nucleating agent and 300-600 ppm of acid acceptor according to mass concentration.
More preferably, the compounding aid comprises 1300ppm of an antioxidant, 1600ppm of a light stabilizer, 2000ppm of a modified nucleating agent and 500ppm of an acid acceptor by mass concentration.
The mass concentration of the composite auxiliary agent is the concentration expressed by the mass per million of each component in the composite auxiliary agent in the mass of polyolefin, and the unit is ppm.
In one embodiment, the modifier is a siloxane.
Preferably, the siloxane comprises (R) 1 ) 3 -Si-OR 2 And (R) 3 O) 3 -Si-R 4 (ii) a Wherein R is 1 Is phenyl or an alkyl radical containing a benzene ring, R 2 Is an alkyl group; r 3 Is an alkyl radical, R 4 Is an alkane group containing a benzene ring.
More preferably, the siloxane comprises methoxytriphenylsilane and trimethoxy (2-phenylethyl) silane.
More preferably, the mass ratio of the methoxytriphenylsilane to the trimethoxy (2-phenylethyl) silane is 1.5-4: 1; more preferably, the mass ratio of methoxytriphenylsilane to trimethoxy (2-phenylethyl) silane is 3.5: 1.
in one embodiment, the modified nucleating agent is prepared by the following method: dissolving a modifier and a nucleating agent in a solvent, reacting for 2-12 h at the temperature of 40-100 ℃, distilling under reduced pressure, and washing with water to obtain the modified nucleating agent; wherein the nucleating agent is a sorbitol nucleating agent and/or a phosphate nucleating agent; the solvent is selected from any one of anhydrous chloroform, toluene, N-dimethylformamide, tetrahydrofuran and acetone.
Preferably, the mass ratio of the added amount of the solvent to the nucleating agent is 15-25: 1; more preferably, the mass ratio of the added amount of the solvent to the nucleating agent is 20: 1.
more preferably, the nucleating agent is a sorbitol based nucleating agent, purchased from GRH-128 of Shanghai Zirun New materials, Inc.
In one embodiment, the antioxidant comprises a primary antioxidant and a secondary antioxidant.
Preferably, the mass ratio of the main antioxidant to the auxiliary antioxidant is 3-7: 8; more preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is 5: 8.
preferably, the primary antioxidant is a hindered phenol antioxidant, and the secondary antioxidant is a phosphite antioxidant.
More preferably, the primary antioxidant is antioxidant 1010 and the secondary antioxidant is antioxidant 168.
In one embodiment, the light stabilizer is a composite hindered amine type light stabilizer.
Preferably, the composite hindered amine light stabilizer consists of a light stabilizer 944 and a light stabilizer 622 in a mass ratio of 1: 1 are compounded. The composite light stabilizer can effectively capture free radicals generated by irradiation or ultraviolet irradiation of the polypropylene material, reduce the probability of yellowing of the material due to degradation, and play a role in light stabilization of the polypropylene material.
In one embodiment, the acid scavenger is selected from at least one of calcium stearate, hydrotalcite, metal soap salt, magnesium stearate, aluminum stearate.
Preferably, the acid scavenger is calcium stearate.
The applicant researches and discovers that when the modifier is methoxy triphenylsilane and trimethoxy (2-phenylethyl) silane, the radiation resistance of the material is favorably improved, and the yellowing index is slightly increased and changed even if the material is placed under the high-temperature and high-humidity condition for 3 months after radiation, which is probably because polar hydroxyl in sorbitol nucleating agent molecules can be partially replaced by the modifier in modification, so that the dispersibility of the sorbitol nucleating agent in polypropylene is improved on one hand; on the other hand, because the radiation can accelerate the formation of free radicals, the aging and yellowing of polyolefin materials are caused, and the performance is rapidly reduced, when the composite auxiliary agent provided by the invention is adopted, the hindered phenol antioxidant and the modified nucleating agent generate a synergistic effect, in the crystallization process, the active group of the sorbitol nucleating agent and long-chain silane form a complexing effect, the modified nucleating agent brings the hindered phenol antioxidant into the crystal nucleus of polyolefin to block the formation of free radicals, slow down the aging of the polyolefin materials, and simultaneously, the modified nucleating agent and a light stabilizer in the system act together to facilitate the high-efficiency conversion of a random molecular chain segment into a spiral structure in the nucleation process, improve the crystallization rate of the nucleating agent, the added methoxytriphenylsilane can be wrapped inside, the added trimethoxy (2-phenylethyl) silane extends to the outside, under the radiation, the components interact with each other, so that not only can free radicals and peroxy radicals generated by irradiation be captured to form a new stable product and promote crystallization, but also absorbed radiation energy can be dispersed inside and outside simultaneously, the excitation energy is transferred inside and outside molecules, and bond breakage is avoided, so that the irradiation resistance of the material is greatly improved, and the yellowing index of the material is increased by a small change value even if the material is placed under the high-temperature and high-humidity condition for 3 months after irradiation. In addition, in the invention, when the mass ratio of the methoxyl triphenyl silane to the trimethoxy (2-phenylethyl) silane is controlled to be 3.5:1, the radiation resistance of the polyolefin material is greatly improved when the polyolefin material is applied to the polyolefin material.
The second purpose of the invention is to provide a preparation method of the composite auxiliary agent, which comprises the steps of putting the antioxidant, the light stabilizer, the modified nucleating agent and the acid acceptor into a mixer, uniformly mixing, carrying out dry-method rolling granulation, crushing and screening to obtain the composite auxiliary agent.
The preparation method of the composite additive adopts dry powder extrusion granulation, and the composite additive granulation method of the invention is a dry extrusion granulation technology without heating and adding any other solvent; the method avoids the defects of solvent bonding and impurity residue possibly caused by wet granulation and possible change of the appearance and performance of the additive after the melting granulation is heated, so that the prepared compound agent has stable product quality and small fluctuation of the effectiveness of the compound additive.
The third purpose of the invention is to provide the application of the composite auxiliary agent on polyolefin. The composite auxiliary agent is applied to polyolefin to produce irradiation-resistant non-woven fabrics, medical masks and protective clothing.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite additive prepared by the invention is applied to polyolefin, and the performance of the composite additive can meet the special material requirements of T/SGX 001-;
(2) when the composite additive prepared by the invention is applied to polyolefin materials, under the action of the modifier, polar hydroxyl groups in sorbitol nucleating agent molecules are partially substituted, so that the dispersibility of the sorbitol nucleating agent in polypropylene is improved, and the radiation resistance of the materials is favorably improved; on the other hand, because the radiation can accelerate the formation of free radicals, the aging and yellowing of polyolefin materials are caused, and the performance is rapidly reduced, when the composite auxiliary agent provided by the invention is adopted, the hindered phenol antioxidant and the modified nucleating agent generate a synergistic effect, in the crystallization process, the active group of the sorbitol nucleating agent and long-chain silane form a complexing effect, the modified nucleating agent brings the hindered phenol antioxidant into the crystal nucleus of the polyolefin to block the formation of free radicals, slow down the aging of the polyolefin materials, and simultaneously, the modified nucleating agent and a light stabilizer in the system mutually cooperate to promote the irregular molecular chain segment to be efficiently converted into a spiral structure in the nucleation process, improve the crystallization rate of the polyolefin, simultaneously, the methoxyl triphenyl silane is wrapped inside, the trimethoxy (2-phenylethyl) silane extends to the outside, not only can capture free radicals generated by the radiation and peroxy radicals to form a new stable product, the crystallization is promoted, the absorbed irradiation energy can be dispersed inside and outside the polyolefin material, the excitation energy is transferred inside and outside the molecule, and the bond fracture is avoided, so that the irradiation resistance of the polyolefin material is improved, and the yellowing index is little increased and changed even if the polyolefin material is placed under the condition of high temperature and high humidity for 3 months after irradiation. Further, in the invention, when the mass ratio of the methoxytriphenylsilane to the trimethoxy (2-phenylethyl) silane is controlled to be 3.5:1 and the methoxytriphenylsilane to the trimethoxy (2-phenylethyl) silane are matched with an antioxidant, an acid acceptor and a light stabilizer, the radiation resistance of the polyolefin material is improved when the methoxytriphenylsilane and the trimethoxy (2-phenylethyl) silane are applied to the polyolefin material.
(3) The composite additive prepared by the invention is applied to polyolefin, is irradiated under the absorbed dose of 20, 30, 40 and 50kGy, has excellent performance indexes, and solves the problem of irradiation degradation of medical PP materials.
Detailed Description
The compounding aid of the present invention and its use in polyolefins are further described below with reference to specific embodiments.
Example 1
This example provides a compounding aid that includes 1000ppm antioxidant, 800ppm light stabilizer, 1000ppm modified nucleating agent, and 200ppm acid scavenger.
The raw materials of the modified nucleating agent comprise the nucleating agent and the modifying agent; the mass ratio of the nucleating agent to the modifying agent is 1.5: 1.
the modifier comprises methoxytriphenylsilane and trimethoxy (2-phenylethyl) silane; the mass ratio of the methoxytriphenylsilane to the trimethoxy (2-phenylethyl) silane is 1.5: 1.
the preparation method of the modified nucleating agent comprises the following steps: dissolving a modifier and a nucleating agent in N, N-dimethylformamide, reacting for 7 hours at the temperature of 80 ℃, distilling under reduced pressure, and washing with water to obtain the modified N-dimethylformamide nucleating agent.
The mass ratio of the addition amount of the solvent to the nucleating agent is 20: 1.
the nucleating agent is a sorbitol nucleating agent and is purchased from GRH-128 of Shanghai Qirun New Material Co.
The antioxidant is prepared from the following components in percentage by mass: 8 antioxidant 1010 and antioxidant 168. Hindered phenol antioxidant
The mass ratio of the light stabilizer is 1: 1 light stabilizer 944 and light stabilizer 622.
The acid absorbent is calcium stearate.
In this embodiment, the preparation method of the composite additive comprises: and (3) putting the antioxidant, the light stabilizer, the modified nucleating agent and the acid absorbing agent into a mixer, uniformly mixing, performing dry-method rolling granulation, and crushing and screening for later use.
The addition ratio of the composite auxiliary agents provided by the examples 2-9 and the comparative examples 1-6 is shown in the following table 1:
table 1 shows the addition ratio of the composite additives provided in examples 1 to 9 and comparative examples 1 to 6
Figure BDA0003714614350000051
In examples 2 to 9 and comparative examples 1 to 6, the same as example 1 was used except that the content ratio of each component in the composite assistant was different from that in example 1.
Example 10 evaluation of Properties
The composite auxiliary agents provided in the examples 1-9 and the comparative examples 1-6 and the polypropylene powder of the original petrochemical MT25 (at 230 ℃, the melt flow rate of 2.16kg is 25g/10min) are melted, extruded and granulated, and the products of the examples 1-9 and the comparative examples 1-6 are tested according to the requirements of T/SGX 001-.
The composite additive of examples 1-9 and comparative examples 1-6 and the original petrochemical MT25 (2.16 kg with a melt flow rate of 25g/10min at 230 ℃) were melted, extruded and pelletized, and the injection molded sample was irradiated under 20, 30, 40 and 50kGy of absorption dose and then placed under high temperature and high humidity (85 ℃ temperature and 85% humidity) for 3 months to be tested for yellow index (GB/T2409), tensile strength (GB/T1040) and impact strength (GB/T1843.1), and the data were recorded, and the specific results are shown in tables 2, 3 and 4.
TABLE 2 yellowness index
Figure BDA0003714614350000061
TABLE 3 tensile Strength
Figure BDA0003714614350000062
Figure BDA0003714614350000071
TABLE 4 impact Strength
Figure BDA0003714614350000072
Compared with the comparative example, the polypropylene sample prepared by each example shows absolute advantage in mechanical property under the same irradiation condition, and the change of the yellow index is smaller and the performance is more excellent than that of the comparative example; in addition, the data of comparative examples 1 to 9 show that when the antioxidant, the light stabilizer and the acid acceptor are used in appropriate proportions, the ratio of the compound to the compound is methoxy triphenyl silane: when the mass ratio of trimethoxy (2-phenylethyl) silane is 3.5:1, the mechanical property and the yellowing index of the prepared sample wafer are in the optimal state.
Through comparison of the results, the radiation-resistant polypropylene resin composition prepared by the modified nucleating agent disclosed by the invention is irradiated under the absorbed dose of 20, 30, 40 and 50kGy, the performance indexes are excellent, and the problem of radiation degradation of medical PP materials is solved.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (10)

1. The composite additive is characterized by comprising an antioxidant, a light stabilizer, a modified nucleating agent and an acid absorbent; the raw materials of the modified nucleating agent comprise the nucleating agent and the modifying agent; the mass ratio of the nucleating agent to the modifying agent is 1.5-10: 1.
2. the composite additive according to claim 1, wherein the mass ratio of the nucleating agent to the modifying agent is 4-7: 1; preferably, the mass ratio of the nucleating agent to the modifying agent is 5: 1.
3. the composite additive according to claim 1, wherein the composite additive comprises 1000-2000 ppm of antioxidant, 800-2000 ppm of light stabilizer, 1000-10000 ppm of modified nucleating agent and 200-700 ppm of acid acceptor by mass concentration; preferably, the composite auxiliary agent comprises 1000-2000 ppm of antioxidant, 1000-2000 ppm of light stabilizer, 1000-5000 ppm of modified nucleating agent and 300-600 ppm of acid acceptor; preferably, the compounding aid comprises 1300ppm of an antioxidant, 2000ppm of a light stabilizer, 2000ppm of a modified nucleating agent and 500ppm of an acid acceptor.
4. The compounding aid of claim 1 or 2, wherein the modifier is a siloxane; preferably, the siloxane comprises (R) 1 ) 3 -Si-OR 2 And (R) 3 O) 3 -Si-R 4 (ii) a Wherein R is 1 Is phenyl or an alkyl radical containing a benzene ring, R 2 Is an alkyl group; r is 3 Is an alkane group or an alkene group containing a benzene ring, R 4 Is an alkyl group; preferably, the siloxane comprises methoxytriphenylsilane and trimethoxy (2-phenylethyl) silane; preferably, the mass ratio of the methoxytriphenylsilane to the trimethoxy (2-phenylethyl) silane is 1.5-4: 1; more preferably, the mass ratio of methoxytriphenylsilane to trimethoxy (2-phenylethyl) silane is 3.5: 1.
5. the composite additive as claimed in claim 1 or 2, wherein the preparation method of the modified nucleating agent is as follows: dissolving a modifier and a nucleating agent in a solvent, reacting for 2-12 h at the temperature of 40-100 ℃, distilling under reduced pressure, and washing with water to obtain the modified nucleating agent; wherein the nucleating agent is a sorbitol nucleating agent and/or a phosphate nucleating agent; the solvent is selected from any one of anhydrous chloroform, toluene, N-dimethylformamide, tetrahydrofuran and acetone.
6. The compounding aid of claim 1 or 2, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant; the light stabilizer is a composite light stabilizer.
7. The compounding aid according to claim 6, wherein the compound light stabilizer is a compound hindered amine light stabilizer.
8. The compounding aid according to claim 1 or 2, wherein the acid scavenger is at least one selected from the group consisting of calcium stearate, hydrotalcite, metal soap salt, magnesium stearate, and aluminum stearate.
9. The preparation method of the composite additive as claimed in any one of claims 1 to 8, wherein the antioxidant, the light stabilizer, the modified nucleating agent and the acid acceptor are put into a mixer, mixed uniformly, rolled and granulated by a dry method, and crushed and sieved to obtain the composite additive.
10. Use of a compounding aid according to any one of claims 1 to 8 or a compounding aid obtained by the process according to claim 9 in polyolefins.
CN202210734104.XA 2022-06-27 2022-06-27 Composite auxiliary agent and preparation method and application thereof Pending CN114891271A (en)

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CN110564054A (en) * 2019-08-30 2019-12-13 合肥科拜耳新材料有限公司 high beta crystal form polypropylene material and preparation method thereof

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CN102146183A (en) * 2010-02-04 2011-08-10 中国石油化工股份有限公司 Beta nucleating agent for polypropylene, preparation method thereof, and beta polypropylene pipe special material prepared from same
CN110564054A (en) * 2019-08-30 2019-12-13 合肥科拜耳新材料有限公司 high beta crystal form polypropylene material and preparation method thereof

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