阅读说明：本技术 一种复合增韧剂、制备方法、应用和高抗冲聚苯乙烯树脂组合物及其制备方法 (Composite toughening agent, preparation method and application thereof, and high impact polystyrene resin composition and preparation method thereof ) 是由 林士文 黄险波 叶南飚 官焕祥 郭少华 李玉虎 黄宝奎 付锦锋 于 2021-02-26 设计创作，主要内容包括：本发明公开了一种复合增韧剂、制备方法、应用和高抗冲聚苯乙烯树脂组合物及其制备方法,所述复合增韧剂,包括以下成分：热塑性弹性体；活性纳米粒子；苯乙烯接枝共聚物；润滑剂。一种高抗冲聚苯乙烯树脂组合物,包括以下成分：高抗冲聚苯乙烯；复合增韧剂；抗氧剂；润滑剂。本发明提供的复合增韧剂,应用于高抗冲聚苯乙烯树脂组合物的增韧,能显著提高高抗冲聚苯乙烯树脂组合物的缺口抗冲击强度,成本低,效果好,可以替代ABS,PC/ABS等用于家用电器等的外壳。(The invention discloses a composite toughening agent, a preparation method and application thereof, and a high impact polystyrene resin composition and a preparation method thereof, wherein the composite toughening agent comprises the following components: a thermoplastic elastomer; an active nanoparticle; styrene graft copolymers; and (3) a lubricant. A high impact polystyrene resin composition comprising the following ingredients: high impact polystyrene; a composite toughening agent; an antioxidant; and (3) a lubricant. The composite toughening agent provided by the invention is applied to toughening of the high impact polystyrene resin composition, can obviously improve the notch impact strength of the high impact polystyrene resin composition, has low cost and good effect, and can replace ABS, PC/ABS and the like for shells of household appliances and the like.)

1. The composite toughening agent is characterized by comprising the following components:

a thermoplastic elastomer;

an active nanoparticle;

styrene graft copolymers;

a lubricant;

an antioxidant.

2. The composite toughening agent according to claim 1, characterized by comprising the following components in parts by weight:

50-70 parts by weight of thermoplastic elastomer;

30-50 parts of active nano particles;

2-5 parts of styrene graft copolymer;

0.7-1.5 parts by weight of a lubricant;

0.3 to 0.5 weight portion of antioxidant.

3. The composite toughener of claim 2, wherein:

the thermoplastic elastomer is a styrene-butadiene-styrene block copolymer.

4. The composite toughener of claim 2, wherein:

the active nano particles are one or a compound of two of calcium carbonate whiskers or calcium sulfate whiskers modified by a silane coupling agent, and the dosage of the silane coupling agent is 0.5-2 wt% of the calcium carbonate whiskers or the calcium sulfate whiskers.

5. The composite toughener of claim 2, wherein:

the average length of the calcium carbonate whisker or the calcium sulfate whisker is 50-70um, and the average diameter is 2-3 um.

6. The composite toughener of claim 2, wherein:

the styrene graft copolymer is a copolymer of styrene grafted maleic anhydride or a copolymer of hydrogenated styrene elastomer-maleic anhydride graft;

the silane coupling agent is selected from KH-550 or KH-560 silane coupling agent;

the antioxidant is selected from one or two of antioxidant 1010 and antioxidant 168;

the lubricant is selected from one or a combination of two of ethylene bis-stearic acid amide and zinc stearate.

7. A method of making a composite toughener according to any of claims 1 to 6, characterized by the steps of:

1) proportionally mixing the calcium carbonate whiskers or the calcium sulfate whiskers with a silane coupling agent at a high speed in a high-speed mixer for 5 minutes to obtain active nanoparticles;

2) the thermoplastic elastomer, the active nano particles, the styrene graft copolymer, the antioxidant and the lubricant are uniformly mixed in a double-roll open mill according to the proportion, and the composite toughening agent is obtained by granulation.

8. Use of a composite toughening agent according to any of claims 1 to 6 for increasing the notched impact strength of a high impact polystyrene resin composition.

9. A high impact polystyrene resin composition comprises the following components in parts by weight:

50-90 parts by weight of high impact polystyrene;

10-50 parts by weight of the composite toughening agent of any one of claims 1 to 6;

0.3 part of antioxidant;

0.7 part by weight of lubricant;

the antioxidant is selected from one or two of antioxidant 1010 and antioxidant 168; the lubricant is selected from one or a combination of two of ethylene bis-stearic acid amide and zinc stearate.

10. The method of preparing the high impact polystyrene resin composition of claim 9:

and extruding and granulating the high impact polystyrene, the composite toughening agent, the antioxidant and the lubricant by using a double screw according to the proportion to obtain the high impact polystyrene resin composition.

Technical Field

The invention belongs to the field of high molecular polymers, and particularly relates to a composite toughening agent, a preparation method and application thereof, a high impact polystyrene resin composition and a preparation method thereof.

Background

The high impact polystyrene is a general resin with good dimensional stability and fluidity, has excellent mechanical balance, is widely applied to the fields of electronic appliances, household appliances, food packaging and the like, and is one of five general plastics. The high impact polystyrene can replace products such as ABS, PC/ABS and the like in many occasions, but because the notch impact strength of the high impact polystyrene is still obviously different from that of ABS, PC/ABS and the like, the application of the high impact polystyrene is limited in occasions requiring ultrahigh impact strength; the common method for improving the impact strength of the composite material is to add thermoplastic elastomers such as SBS, SEBS and the like as toughening agents, but meanwhile, the SBS and the SEBS are high in price, so that the cost of the composite material is obviously increased, and the cost performance advantage of the composite material is reduced.

Inorganic fillers are generally used for cost reduction of resins, while thermoplastic elastomers are used as toughening agents, for example, in some preparation methods, 1-5% of fillers are added only for cost reduction, but the toughness of the materials is not good; in another technique, the formula of the polystyrene toughening master batch uses 5-15% of compatilizer: at least one of ethylene propylene diene monomer-maleic anhydride graft, POE-maleic anhydride graft, and hydrogenated styrene elastomer-maleic anhydride graft has poor impact strength.

Disclosure of Invention

The invention aims to provide a composite toughening agent, which is applied to toughening of a high impact polystyrene resin composition, can obviously improve the notch impact strength of the high impact polystyrene resin composition, has low cost and good effect, and can replace ABS, PC/ABS and the like to be used for shells of household appliances and the like.

Further, there is a need for a method of preparing the above composite toughener.

Further, there is a need to provide for the use of the above-described composite tougheners.

Furthermore, the invention also provides a high impact polystyrene resin composition which has good comprehensive performance, high notch impact strength and low cost, is suitable for shells of household appliances such as televisions, water dispensers, air conditioners and the like, and has higher cost performance than ABS/PC/ABS.

Further, there is a need for a method of preparing the above high impact polystyrene resin composition.

A composite toughening agent comprises the following components:

a thermoplastic elastomer;

an active nanoparticle;

styrene graft copolymers;

a lubricant;

an antioxidant.

Preferably, the composite toughening agent comprises the following components in parts by weight:

50-70 parts by weight of thermoplastic elastomer;

30-50 parts of active nano particles;

2-5 parts of styrene graft copolymer;

0.7-1.5 parts by weight of a lubricant;

0.3 to 0.5 weight portion of antioxidant. More preferably, the composite toughening agent comprises the following components in parts by weight:

60 parts by weight of a thermoplastic elastomer;

40 parts of active nano particles;

2 parts by weight of a styrene graft copolymer;

1.1 parts by weight of a lubricant;

0.4 part of antioxidant.

Preferably, the thermoplastic elastomer is a styrene-butadiene-styrene block copolymer having a styrene to butadiene molar ratio of about 3: 7.

preferably, the active nano particles are calcium carbonate whiskers or calcium sulfate whiskers modified by a silane coupling agent, and the amount of the silicon coupling agent is 0.5-2 wt% of the calcium carbonate whiskers or the calcium sulfate whiskers.

The calcium carbonate whisker or the calcium sulfate whisker is micro-nano short fiber grown from high-purity single crystal, and can be used for improving the strength of resin and reducing the shrinkage rate of the resin.

The preparation method of the active nano-particle comprises the following steps:

and proportionally mixing the calcium carbonate whiskers or the calcium sulfate whiskers with the silane coupling agent in a high-speed mixer for 5 minutes to obtain the active nanoparticles.

Preferably, the calcium carbonate whiskers or calcium sulfate whiskers have an average length of 50 to 70um and an average diameter of 2 to 3 um.

Preferably, the styrene graft copolymer is a styrene-maleic anhydride graft copolymer or a hydrogenated styrene elastomer-maleic anhydride graft copolymer, and the graft ratio is about 18%;

the silane coupling agent is selected from KH-550 or KH-560 silane coupling agent;

the antioxidant is selected from one or two of antioxidant 1010 and antioxidant 168; the lubricant is selected from one or a combination of two of ethylene bis-stearic acid amide and zinc stearate.

The preparation method of the composite toughening agent comprises the following steps:

1) proportionally mixing the calcium carbonate whiskers or the calcium sulfate whiskers with a silane coupling agent at a high speed in a high-speed mixer for 5 minutes to obtain active nanoparticles;

2) the thermoplastic elastomer, the active nano particles, the styrene graft copolymer, the antioxidant and the lubricant are uniformly mixed in a double-roll open mill according to the proportion, and the composite toughening agent is obtained by granulation.

Preferably, the process conditions of the two-roll open mill are that the temperature is 80-120 ℃, and the rotating speed is 60-100 r/min; more preferably, the process conditions of the two-roll mill are a temperature of 100 ℃ and a rotation speed of 80 r/min.

The composite toughening agent is applied to improving the impact strength of the high impact polystyrene resin composition, so that the notch impact strength of the high impact polystyrene resin composition can be obviously improved, the better strength is kept, and the shrinkage rate of the material is reduced.

A high impact polystyrene resin composition comprises the following components in parts by weight:

50-90 parts by weight of high impact polystyrene;

10-50 parts of the composite toughening agent;

0.3 part of antioxidant;

0.7 part by weight of lubricant;

preferably, the high impact polystyrene resin composition comprises the following components in parts by weight:

85 parts by weight of high impact polystyrene;

15 parts by weight of the composite toughening agent;

0.3 part of antioxidant;

0.7 part by weight of lubricant.

The antioxidant is selected from one or two of antioxidant 1010 and antioxidant 168;

the lubricant is selected from one or a combination of two of ethylene bis-stearic acid amide and zinc stearate.

The preparation method of the high impact polystyrene resin composition as described above:

and extruding and granulating the high impact polystyrene, the composite toughening agent, the antioxidant and the lubricant by using a double screw according to the proportion to obtain the high impact polystyrene resin composition.

Preferably, the double-screw extrusion condition is that the temperature is 180-220 ℃, and the screw rotating speed is 200-800 r/min. More preferably, the twin-screw extrusion condition is that the temperature is 180-220 ℃, and the screw rotating speed is 600 r/min.

According to the scheme, by optimizing the proportion of the combined thermoplastic elastomer, a more appropriate compatilizer is preferably selected, meanwhile, the nano filler with a specific particle size has partial compatibility, the combination of the nano filler and resin is not too strong or too weak, and when the nano filler is impacted by external force, a great number of micro-cavities are rapidly formed to dissipate a great amount of energy; too little nano filler (high content of toughening agent) can not form enough micro-cavities, while too much filler (low content of toughening agent) destroys the continuity of the resin matrix and does not have super-toughness performance; the impact strength of the HIPS resin can exceed 20KJ/m of that of the general ABS²The highest can reach 37.8KJ/m²The ultra-high impact strength of the rubber can replace ABS and PC/ABS for cost reduction; and the fluidity of HIPS is better than that of ABS and PC/ABS, which is beneficial to the molding of the product and the reduction of the internal stress.

Compared with the prior art, the composite toughening agent prepared by the invention is prepared by uniformly mixing the thermoplastic elastomer, the active nano particles, the styrene graft copolymer, the antioxidant and the lubricant in a double-roller open mill and granulating. The active nano particles are prepared from calcium carbonate whiskers or calcium sulfate whiskers with specific particle sizes through a silane coupling agent, the notch impact strength of the high impact polystyrene resin composition can be remarkably improved, and the prepared high impact polystyrene resin composition is excellent in flow property, lower in cost, higher in cost performance and applicable to the fields of household appliances, electronic appliances and the like.

Detailed Description

In order that those skilled in the art will better understand the disclosure, the present invention will be further described in detail with reference to the following specific examples.

The starting materials for the inventive and comparative examples are commercially available.

High impact polystyrene: PH-88, Zhenjiangqi beauty works Ltd

Styrene graft copolymer: styrene-maleic anhydride-grafted copolymer, SMA 700, graft ratio 18%, Jiaxing Hua Wen chemical Co., Ltd

POE graft maleic anhydride graft, W1A, graft rate 1%, Xiamen Esse plastics science and technology ltd;

EPDM grafted maleic anhydride graft, DM-7, graft 0.8%, Dow chemical company;

hydrogenated styrene elastomer-maleic anhydride graft copolymer, FG-1901, graft rate 1.5%, Keteng chemical.

Nano calcium carbonate: AC-05N, particle size 5um, Guangdong Xianglong science and technology Co., Ltd;

thermoplastic elastomer: styrene-butadiene-styrene Block copolymer (SBS) model SBS YH792E, Balng division of petrochemical Co., Ltd., China

Calcium carbonate whiskers, NP-CW2, Shanghai Tanshu trade Co., Ltd., average length 50 μm, average diameter 2 μm;

glass fiber powder, MF-T100W, Yinuo New Material science and technology Limited, Jingjiang, with an average length of 130 μm and an average diameter of 13 μm;

calcium sulfate whisker, DL-40H, Shenzhen Shenbang New energy materials Limited, average length 70 μm, average diameter 3 μm.

Nano calcium carbonate, AC-05N, particle size 5um, Guangdong Xianglong science and technology Co., Ltd

Silane coupling agent: KH-550, KH-560 Nanjing warp-weft chemical Co., Ltd

Antioxidant: antioxidant 1010, Beijing very easily available chemical Co., Ltd

Antioxidant: antioxidant 168, Beijing very easily available chemical Co., Ltd

Lubricant EBS: shangxi Macro chemical Limited

Lubricant zinc stearate: shangxi Macro chemical Limited

POE graft maleic anhydride graft W1A, graft ratio 1%, Xiamen Esse plastics science and technology Co

Ethylene propylene diene monomer-maleic anhydride graft: FG-1901, graft rate 1.5%, Koteng chemical

Hydrogenated styrene elastomer-maleic anhydride graft copolymer FG-1901, graft rate 1.5%, Koteng chemical

Example 1

Preparation of composite toughening agent 1:

1) mixing the calcium carbonate whisker A and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 1 is obtained through granulation.

Example 2

Preparation of composite toughening agent 2:

1) mixing the calcium sulfate whisker and a silane coupling agent KH560 in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 0.5 wt% of the calcium sulfate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 80 ℃, the rotating speed is 100r/min, and the composite toughening agent 2 is obtained through granulation.

Example 3

Preparation of composite toughening agent 3:

1) mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 2 wt% of the calcium carbonate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 120 ℃, the rotating speed is 60r/min, and the composite toughening agent 3 is obtained through granulation.

Example 4

Preparation of composite toughening agent 4:

1) mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 4 is obtained through granulation.

Example 5

Preparation of composite toughening agent 5:

1) mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 5 is obtained through granulation.

Example 6

1) Mixing glass fiber powder and a silane coupling agent at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the glass fiber powder;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nano particles, the styrene-grafted maleic anhydride copolymer (compatilizer), the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 6 is obtained through granulation.

Example 7

1) Mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) thermoplastic elastomer (SBS), active nano-particles, copolymer (compatilizer) of EPDM grafted maleic anhydride graft, antioxidant 1010, antioxidant 168, lubricant EBS and lubricant zinc stearate are uniformly mixed in a double-roll open mill according to the weight ratio shown in Table 1, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 7 is obtained by granulation.

Example 8

1) Mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) according to the weight ratio shown in table 1, the thermoplastic elastomer (SBS), the active nanoparticles, the copolymer (compatilizer) of the POE grafted maleic anhydride graft, the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed in a double-roll open mill, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 8 is obtained through granulation.

Example 9

1) Mixing the calcium carbonate whisker and a silane coupling agent KH550 at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the calcium carbonate whisker;

2) thermoplastic elastomer (SBS), active nano particles, hydrogenated styrene elastomer-maleic anhydride graft copolymer (compatilizer), antioxidant 1010, antioxidant 168, lubricant EBS and lubricant zinc stearate are uniformly mixed in a double-roll mill according to the weight ratio shown in Table 1, the process conditions of the double-roll mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 9 is obtained by granulation.

Example 10

1) Mixing nano calcium carbonate and a silane coupling agent at a high speed in a high-speed mixer for 5 minutes to obtain active nano particles, wherein the dosage of the silane coupling agent is 1 wt% of the nano calcium carbonate;

2) thermoplastic elastomer (SBS), active nano particles, styrene grafted maleic anhydride copolymer (compatilizer), antioxidant 1010, antioxidant 168, lubricant EBS and lubricant zinc stearate are uniformly mixed in a double-roll open mill according to the weight ratio shown in Table 1, the process conditions of the double-roll open mill are that the temperature is 100 ℃, the rotating speed is 80r/min, and the composite toughening agent 12 is obtained by granulation.

TABLE 1 formulation of composite toughener 1-10

Experimental examples 1 to 14

The prepared composite toughening agent 1 is used in high impact polystyrene resin to respectively prepare different high impact polystyrene resin compositions.

The high impact polystyrene, the composite toughening agent, the antioxidant 1010, the antioxidant 168, the lubricant EBS and the lubricant zinc stearate are uniformly mixed according to the weight parts shown in the tables 2 and 3, and then the mixture is extruded and granulated by using a double screw, wherein the double screw extrusion temperature is 180-220 ℃, and the screw rotation speed is 600r/min, so as to obtain the high impact polystyrene resin composition.

TABLE 2 formulation of high impact polystyrene resin composition TABLE-1

TABLE 3 Experimental examples high impact polystyrene resin composition formulation TABLE-2

	Experimental example 11	Experimental example 12	Experimental example 13	Experimental example 14
					Kinds of composite toughening agents	Composite toughening agent 1	Composite toughening agent 1	Composite toughening agent 2	Composite toughening agent 2
High impact polystyrene dosage	90	70	60	50
					Amount of composite toughening agent	10	30	40	50
The amount of antioxidant 1010 is	0.1	0.1	0.1	0.1
					Antioxidant 168 amount	0.2	0.2	0.2	0.2
EBS dosage of lubricant	0.5	0.5	0.5	0.5
					Amount of zinc stearate used as lubricant	0.2	0.2	0.2	0.2

The high impact polystyrene resin compositions obtained in Experimental examples 1-14 were subjected to the following property tests, and the results are shown in Table 4.

Notched impact strength: ISO 180, injection molding notch, and testing at normal temperature.

Flexural modulus: ISO 178-1-2010, test rate 2 mm/min.

Shrinkage rate: measured according to ISO294-4-2003

TABLE 4 composition Performance test Table

The above performance parameters indicate that the impact strength of the high impact polystyrene is about 10KJ/m²The flexural modulus is 2000MPa, and the shrinkage rate is about 0.56%; SBS is typically added as a toughening agent to increase toughness, but will reduce flexural modulus; the cost is reduced by adding mineral powder such as calcium carbonate, but the impact strength of the material is reduced, and the shrinkage rate of the material is not obviously reduced. The composite toughening agent is formed by using the whiskers and the SBS, has higher toughening efficiency when the SBS with the same content is used, enables the material to keep better flexural modulus, can reduce the shrinkage rate of the material due to the characteristic of the length-diameter ratio, and has obvious comprehensive advantagesAnd (4) potential.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.