CN111484702A

CN111484702A - Low-shrinkage precipitation-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof

Info

Publication number: CN111484702A
Application number: CN201911322086.9A
Authority: CN
Inventors: 郭鑫; 赵武学; 贾宇冲
Original assignee: Sichuan Xinda Enterprise Group Co ltd
Current assignee: Sichuan Xinda Enterprise Group Co ltd
Priority date: 2019-12-20
Filing date: 2019-12-20
Publication date: 2020-08-04

Abstract

The halogen-free flame retardant ABS composite material is composed of raw materials, by mass, 23-68.4% of ABS, 1-5% of flame retardant synergist, 15-30% of phosphorus-nitrogen flame retardant, 20-30% of glass fiber, 2-10% of compatilizer, 0.4-1% of antioxidant and 0.2-1% of lubricant.

Description

Low-shrinkage precipitation-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a low-shrinkage precipitation-resistant halogen-free flame-retardant ABS composite material and a preparation method thereof.

Background

The ABS (acrylonitrile-butadiene-styrene copolymer) has the advantages of three monomers, so the ABS has good comprehensive mechanical properties, heat resistance, oil resistance, wear resistance, stable size and excellent processing performance, is widely applied to the fields of automobiles, household appliances, food, medical treatment, rail transit, aerospace and the like, the strength, rigidity and heat distortion temperature of the glass fiber reinforced ABS material can be obviously improved, but the ABS has an oxygen index of only 18.2 and belongs to the flammable class, so the application of the ABS in some special fields is greatly limited, and most of the ABS can be subjected to flame retardant modification when in use.

The intumescent flame retardant is a flame retardant system which is mostly used for halogen-free flame retardant ABS materials, common intumescent flame retardants include ammonium polyphosphate, melamine polyphosphate and the like, and although the intumescent flame retardant has a good effect, the intumescent flame retardant has low decomposition temperature and high water absorption rate, is easy to hydrolyze and precipitate, further influences the appearance and flame retardant property of the material, and has high addition amount. Therefore, the addition amount is reduced through reasonable compound flame retardant, so that the cost is reduced.

For the glass fiber reinforced material, floating fibers are generally easily generated on the surface, so that the appearance of a finished piece is influenced, and the glass fiber material is oriented along the flow direction during processing, so that the transverse shrinkage rate and the longitudinal shrinkage rate are inconsistent, so that the warping deformation of a product is caused, and the application of ABS is limited.

In view of the above, there is a need for a low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material.

Disclosure of Invention

The invention overcomes the defects in the prior art, and provides a low-shrinkage and precipitation-resistant halogen-free flame-retardant ABS composite material which has excellent flame retardant property, precipitation resistance, high dimensional stability, no warping deformation, excellent surface property, no floating fiber, strong practicability, low cost, simple preparation method and easy industrial production, and adopts the following technical scheme:

the detailed formula of the raw materials comprises the following components in percentage by mass:

ABS23～68.4%

15 to 30 percent of phosphorus-nitrogen flame retardant

1-5% of flame-retardant synergist

20 to 30 percent of glass fiber

2 to 8 percent of compatilizer

0.4 to 1 percent of antioxidant

0.2-1% of a lubricant.

1. The ABS is at least one of homopolymerized ABS and copolymerized ABS, and the melt index of the ABS is 1-30g/10min (230 ℃, 2.16 Kg).

2. The flame-retardant synergist is at least one of zinc borate, boron nitride, zinc oxide and montmorillonite.

3. The phosphorus-nitrogen flame retardant consists of one or more of piperazine pyrophosphate and melamine polyphosphate.

4. The glass fiber is formed by compounding alkali-free chopped glass fibers and profiled fibers according to the proportion of 3-5: 1-2, the section of the profiled glass fiber is oval, and the profile ratio of the profiled glass fiber is 2-10.

5. The compatilizer is at least one of ABS grafted maleic anhydride (ABS-g-MAH), styrene-acrylonitrile free copolymer (SAN) and ABS-g-GMA.

6. The antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.

7. The lubricant is one or more of calcium stearate, EBS and PETS.

8. The preparation process comprises the following steps: adding ABS, phosphorus-nitrogen flame retardant, flame-retardant synergist, lubricant, antioxidant and compatilizer into a high-speed stirrer in proportion, uniformly mixing, adding into a double-screw extruder, adding glass fiber serving as a side feeding port, extruding, bracing, water-cooling, granulating and homogenizing to obtain the low-shrinkage, precipitation-resistant, halogen-free and flame-retardant glass fiber reinforced ABS composite material, wherein the processing temperature is 220-245 ℃.

9. The invention has the beneficial effects that:

(1) the low-shrinkage precipitation-resistant halogen-free flame-retardant glass fiber reinforced ABS material solves the problems of easy precipitation, poor heat resistance, large addition amount and the like of the traditional intumescent flame retardant by using the precipitation-resistant phosphorus-nitrogen flame retardant with better thermal property and adding a proper amount of flame-retardant synergist, further reduces the material cost through the compounding synergistic effect,

(2) the invention greatly reduces the shrinkage rate of the material, improves the dimensional stability of the material, can effectively prevent the material from warping and deforming by compounding the chopped glass fiber and the special-shaped glass fiber,

(3) the low-shrinkage and precipitation-resistant halogen-free flame-retardant glass fiber reinforced ABS material has outstanding flame retardant performance, has low fiber floating on the surface of the material, good compatibility with glass fiber, more excellent mechanical property and simple preparation process by reasonably using the lubricant and the compatilizer, and is beneficial to large-scale industrial production.

Detailed Description

The low-shrinkage precipitation-resistant halogen-free flame-retardant ABS composite material comprises the following components in percentage by mass:

ABS23～68.4%

15 to 30 percent of phosphorus-nitrogen flame retardant

1-5% of flame-retardant synergist

20 to 30 percent of glass fiber

2 to 8 percent of compatilizer

0.4 to 1 percent of antioxidant

0.2-1% of a lubricant.

1 preferably, the ABS is at least one of homopolymerized ABS and copolymerized ABS, and the melt index of the ABS is 1-30g/10min (230 ℃, 2.16 Kg).

2 preferably, the flame-retardant synergist is at least one of zinc borate, boron nitride, zinc oxide and montmorillonite.

3 preferably, the phosphorus-nitrogen flame retardant is composed of one or more of piperazine pyrophosphate and melamine polyphosphate, and more preferably, the piperazine pyrophosphate is from Jinshi source, Inc., and the melamine polyphosphate is ME L APUR 200 from Pasteur.

Preferably, the glass fiber is formed by compounding alkali-free chopped glass fiber and profiled fiber according to the proportion of 3-5: 1-2, the section of the profiled glass fiber is oval, the profiled glass fiber has the profile ratio of 2-10, the melt has better flow stability, and the appearance problems of surface floating fiber, flow marks and the like caused by unstable flow are reduced.

5 preferably, the compatilizer is at least one of ABS grafted maleic anhydride, polyethylene grafted maleic anhydride and PP-g-GMA.

Preferably, the antioxidant is prepared by compounding a hindered phenol antioxidant and a phosphite antioxidant according to the proportion of 1:1, and further preferably, the hindered phenol antioxidant and the phosphite antioxidant are 1010 and DSTP of basf respectively.

7. Preferably, the lubricant is one or more of calcium stearate, EBS and PETS.

8. Preferably, in the preparation process: adding ABS, a phosphorus-nitrogen flame retardant, a flame-retardant synergist, a lubricant, an antioxidant and a compatilizer into a high-speed stirrer in proportion, uniformly mixing, adding into a double-screw extruder, adding glass fiber serving as a side feeding port, extruding, bracing, water-cooling, granulating and homogenizing to obtain the low-shrinkage and precipitation-resistant halogen-free flame-retardant glass fiber reinforced ABS composite material, wherein the processing temperature is 220-245 ℃.

The present invention will be further described with reference to specific examples.

The formulation compositions of the examples and comparative examples are shown in Table 1

TABLE 1 formulation composition (in mass%) of examples and comparative examples

Raw materials	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2
							ABS	44.4	40	43.2	37.3	41.3	43.2
Phosphorus-nitrogen flame retardant	15	30	22	25	25	22
							Flame-retardant synergist	5	1	3	4	0	3
Compatilizer	10	2	6	8	8	6
							Glass fiber	20	20	20	20	20	25
Profiled fiber	5	5	5	5	5	0
							Lubricant agent	0.2	1	0.3	0.3	0.3	0.3
Antioxidant agent	0.4	1	0.5	0.4	0.4	0.5

The lubricant used in table 1 is calcium stearate, the compatibilizer is ABS graft maleic anhydride, the antioxidant used is 1010 and the ratio of DSTP is 1:2, and the flame retardant synergist used is zinc borate.

The raw materials are weighed according to the proportion, added into a high-speed stirrer and uniformly mixed, then added into a double-screw extruder, extruded, pulled into strips, cooled by water and granulated to obtain the low-shrinkage and precipitation-resistant halogen-free flame-retardant glass fiber reinforced ABS composite material, and the processing temperature is 220-240 ℃.

The composite materials obtained after processing were tested by the test standards shown in table two, and table 3 shows the test results of the corresponding examples and comparative examples.

Detecting items	Unit of	Test standard
			Tensile strength	Mpa	ISO527-2
Flexural modulus	Mpa	ISO 178
			Impact strength of simply supported beam notch	Kj/m2	ISO 179
Flame retardant properties	CLASS	UL 94

Detecting items

Example 1

Example 2

Example 3

Example 4

Comparative example 1

Comparative example 2

Tensile strength

93.6

98.8

97.6

95.8

95.5

99.8

Flexural modulus

6200

6978

6482

6582

6652

6998

Impact strength of simply supported beam notch

8.9

4.9

7.8

8.8

7.3

8.2

Flame retardant Property (1.6 mm)

V-2

V-0

V-1

V-0

Whether or not warping or deformation

Whether or not

Is that

Whether to float the fiber

Whether or not

It can be seen from table 3 that, as shown in comparative example 1, the flame retardant property of the material is reduced to a certain extent due to the absence of the flame retardant synergist, and as shown by data, the addition of the flame retardant synergist not only can improve the flame retardant property of the material, but also can reduce the addition amount of the flame retardant to a certain extent, mainly because the flame retardant synergist has the function of assisting char formation, a more compact char layer is formed, and the flame retardant property is improved, and as compared with comparative example 2, it can be found that after the special-shaped glass fiber is used, the warping deformation of the material is obviously improved, the dimensional stability is improved, and mainly the special-shaped glass fiber can effectively avoid isotropy, so that the flow direction orientation of the glass fiber is reduced.

It should be understood by those skilled in the art that various changes and modifications can be made to the above embodiments without departing from the scope of the present invention, and any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention are within the scope of the present invention.

Claims

1. A low-shrinkage, precipitation-resistant and halogen-free flame-retardant ABS composite material is characterized in that: the material is composed of the following raw materials by mass percent:

ABS 23～68.4%

15 to 30 percent of phosphorus-nitrogen flame retardant

1-5% of flame-retardant synergist

15 to 30 percent of glass fiber

2 to 10 percent of compatilizer

0.4 to 1 percent of antioxidant

0.2-1% of a lubricant.

2. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the ABS is one of low gel content, medium gel content and high gel content, and the melt index of the ABS is 1-30g/10min (220 ℃, 5 Kg).

3. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the flame-retardant synergist is at least one of zinc borate, boron nitride, zinc oxide and montmorillonite.

4. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the phosphorus-nitrogen flame retardant consists of one or more of piperazine pyrophosphate and melamine polyphosphate.

5. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the glass fiber is formed by compounding alkali-free chopped glass fiber and profiled fiber according to the proportion of 3-5: 1-2, the section of the profiled glass fiber is oval, and the profile ratio of the profiled glass fiber is 2-10.

6. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the compatilizer is at least one of ABS grafted maleic anhydride (ABS-g-MAH), styrene-acrylonitrile free copolymer (SAN) and ABS-g-GMA.

7. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.

8. The low-shrinkage, precipitation-resistant, halogen-free, flame-retardant ABS composite material of claim 1, wherein: the lubricant is one or more of calcium stearate, EBS and PETS.

9. The low-shrinkage precipitation-resistant halogen-free flame-retardant ABS composite material as recited in any one of claims 1 to 8, characterized in that: the preparation method comprises the following preparation processes: adding ABS, a phosphorus-nitrogen flame retardant, a flame-retardant synergist, a lubricant, an antioxidant and a compatilizer into a high-speed stirrer in proportion, uniformly mixing, adding into a double-screw extruder, adding glass fiber serving as a side feeding port, extruding, bracing, water-cooling, granulating and homogenizing to obtain the low-shrinkage and precipitation-resistant halogen-free flame-retardant glass fiber reinforced ABS composite material, wherein the processing temperature is 220-245 ℃.