CN101885894B - Modified abs resin and preparation method thereof - Google Patents

Abstract

The invention relates to a modified ABS (Acrylonitrile Butadiene Styrene) resin and a preparation method thereof, which mainly solve the problem of the impact performance of low ABS resin by using the traditional continuous bulk method in the prior art. In the invention, through adopting the technical scheme of blending 10-90 parts of ABS resin in the bulk method, and 9-89 parts of ABS resin I and 1-10 parts of ABS resin II in an emulsion method to extrude to prepare the ABS resin, the invention excellently solves the problem and can be applied to industrial production for ABS resin modification.

Description

Modified ABS resin and preparation method thereof

Technical field

The present invention relates to a kind of modified ABS resin and preparation method thereof.

Background technology

ABS has two complicated phase structures; Be rubber phase and matrix resin; Combine the premium properties of acrylonitritrile-styrene resin and polyhutadiene; Possess that shock resistance is good, surface hardness is high, dimensional stabilizing, chemical resistant properties and good electrical property, be easy to excellent comprehensive performances such as moulding and mechanical workout, be widely used at aspects such as electronics, instrument, automobiles.

The industrial main method of ABS has emulsion graft polymerization polyhutadiene and acrylonitritrile-styrene resin (SAN) blending method and continuous bulk polymerization method.The former be two step method intermittently, half-continuous process production, the cycle of operation is short, it is fast to switch kind, and the handiness of cost and customizable is arranged, foreign matter content high (salt, tensio-active agent) makes through postorder blending granulation in the product; The latter is step continuous processing production, and the cycle of operation is long, and production cost is lower, environmental protection, and product is pure, but it is slow to switch kind, and the technology flexibility ratio is limited, and kind is limited.Because of differences such as rubber content, form, size and distribution, two-phase interface cohesive forces, mechanics of both products and processing characteristics are also different.

Generally speaking, rubber size is 0.03～0.5 μ m among the emulsion method ABS, and rubber size is 0.5～10 μ m among the substance law ABS.Among the substance law ABS rubber grain embedding matrix resin SAN, to such an extent as to the apparent volume of rubber in matrix resin increases, help improving rubber toughened effect.Yet, receive rubber in vinylbenzene, vinyl cyanide, to dissolve limited and the polymerization system viscosity limits, rubber content generally is controlled in 15% among the substance law ABS, is no more than 20% (like US5166261) at most, has limited impact property.In addition, ABS compares with emulsion method, and its stretching and bending property are on the low side.

Introduce rubber and can improve the brittle rupture toughness of material.ABS is typical rubber toughened modified polymeric material.Rubber toughened mechanism mainly contains two kinds: shear yielding and crazing mechanism.Big rubber particles can cause crazing, and small-particle can cause shear yielding.Contain bimodal in the matrix resin or multimodal distribution rubber particles, can produce the coordination plasticizing effect, promptly two kinds of mechanism play a role simultaneously.Discover (Souheng Wu; Polymer Engineering and Sicence; 1991; 30 (13): 753-761), this synergistic effect is the most obvious among the SAN, promptly can make the shock resistance of ABS be higher than the toughening effect of any single particle size rubber particles when suitable at two kinds, the ratio of multiple particle diameter particle.In addition, the small particle size rubber grain is favourable to the glossiness that improves ABS, and big particle diameter rubber grain is favourable to the ABS that is used for inferior finished product.

The known ABS that has the distribution of " bimodal " rubber size through polymerization technique and two kinds of means adjustings of blend can obtain best material physical property (like US3509237, US3576910, US3663656, US3825621, US42502717, US5240993, US649246 etc.), also discloses the good comprehensive properties " three peaks " ABS of distribution recently.

Mention through melt blending among the US4713420 of Dow Chemical house journal and extruding that styrene-acrylonitrile (SAN) multipolymer that ABS that substance law, emulsion method are made and substance law make blend in proportion prepares the method for three peak distribution ABS.The substance law ABS acrylonitrile content that it uses is 22～30%, rubber content is that 0.5～8 μ m, resistance to impact shock are 53.3～346.7J/m as 7wt%～16.2wt%, rubber size; Low particle size emulsion method ABS acrylonitrile content is 28%, and rubber content is that 49wt%, rubber size are 0.1 μ m; Big particle diameter emulsion method ABS glue content is that 45.9wt%, particle diameter are that 0.1 μ m and 1.0 μ m rubber ratio of componentss are 36/64, and also having a kind of big particle diameter emulsion method ABS glue content is that 44.8wt%, particle diameter are that 0.1 μ m and 0.78 μ m rubber ratio of components are 56/44; The substance law SAN copolymerization matrix resin weight-average molecular weight of using is 85000 and 155000.Instance analysis shows that Zong control when glue content is 17wt% in the blended ABS, the blend bimodal distribution ABS that makes with two kinds of different-grain diameter emulsion method ABS increases with macrobead, and shock resistance rises, and glossiness edges down.But the blend bimodal distribution ABS shock resistance with big particle diameter substance law ABS and low particle size emulsion method ABS make rises the glossiness rapid drawdown.Blend three peak distribution ABS glossiness that big particle diameter substance law ABS of part or low particle size emulsion method ABS make can improve or shock resistance can increase as substituting with big particle diameter emulsion method ABS.In addition, use gel content can reach 459J/m as the three peak distribution ABS shock resistances that 45.9wt% big particle diameter emulsion method ABS and substance law ABS blend make, glossiness is half the less than low particle size emulsion method ABS's; If when the total glue content of control was 14wt%, the three peak distribution ABS shock resistances that then make can reach 251J/m, glossiness is half the less than low particle size emulsion method ABS's.Be not difficult to find out, used high glue powder ABS in this patent, and must be condensed into the ABS that contains big small particle size rubber distribution.This type high glue powder ABS complex manufacturing is difficult to find its trace on the market, even have, its price is also very expensive.So non-ABS manufacturing enterprise especially, sets foot in ABS processing and uses enterprise and generally be difficult to the method for using this patent to provide.

Provide preparation to have three peak distribution ABS methods of good gloss degree, low gloss susceptibility among the US5041498 of Dow Chemical house journal [is CN90110250.4 (uncommitted so far) at the China's Mainland application number].Rubber is butylbenzene (93/7) multipolymer among the bimodal distribution emulsion method ABS that adopts, and content is 47%wt, contains the micelle of volume average particle size 0.15 μ m and 0.55 μ m; Rubber is polyhutadiene among the substance law ABS, and content is 7.5%wt, contains the micelle of volume average particle size 0.75 μ m, and grafts and rubber weight ratio are 0.6.Embodiment result shows that total rubber content is controlled at below the 14%wt among the three peak distribution ABS, adds an amount of substance law ABS, and the melting index of three peak distribution ABS is increased, and the gloss susceptibility reduces or the gloss gradient reduces.If increase substance law rubber grain content to＞30%wt, then the gloss susceptibility rises or the gloss gradient increases.Be butylbenzene (70/30) block glue as if rubber among the substance law ABS is changed into, then the gloss susceptibility rises or the increase of gloss gradient.If control total rubber content is 7.5%wt, then increase with substance law ABS content, the gloss susceptibility rises or the gloss gradient increases.If control total rubber content is 12%wt, then increase with substance law ABS content, rising of gloss susceptibility or the increase of gloss gradient are fast when being 7.5%wt than total rubber content.Processing has directive significance though these results are to ABS; But because of above-mentioned same reason, and the ratio that substance law ABS rubber particles accounts for whole rubber particles in this patent is lower than 30%, on cost, do not have advantage; Shock strength does not improve yet, and is unfavorable for that business enterprise expand uses.

Summary of the invention

One of technical problem to be solved by this invention is the substance law ABS resin impact property problem of lower that exists in the prior art, and a kind of new modified ABS resin is provided.This modified ABS resin has the preparation raw material and is easy to get the advantage that impact property is excellent.Two of technical problem to be solved by this invention is preparing methods that the ABS resin that one of a kind of and technical solution problem adapt will be provided.

In order one of to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of ABS resin comprises following component in parts by weight:

A) 10～90 parts of continuous bulk ABS resins, wherein acrylonitrile content is 20～30% by weight percentage, and butadiene content is 5～20%, and styrene content is 60～70%;

B) 10～90 parts of emulsion method ABS resins comprise following component by weight percentage:

(1) 9～89 part of emulsion method ABS resin I, wherein acrylonitrile content is 22～30% by weight percentage, butadiene content 14～25%, styrene content is 50～60%;

(2) 1～10 parts of emulsion method ABS resin II, wherein acrylonitrile content is 7～15% by weight percentage, butadiene content 50～80%, styrene content is 13～35%;

C) 0.01～1 part of oxidation inhibitor.

In the technique scheme; Said substance law ABS resin parts by weight are 20～80 parts, and shock strength is at 100～220J/m, and the particle size range of rubber particles is 0.1～10 μ m; Volume average particle size 0.1～3 μ m, the weight-average molecular weight of external phase SAN is 130000～180000.Said emulsion method ABS resin I parts by weight are 20～80 parts; Shock strength is at 130～500J/m; The particle size range of rubber particles is 0.1～5 μ m, volume average particle size 0.1～1 μ m, and wherein the particle of particle diameter between 0.2～1 μ m accounts for the rubber particles TV more than 60%; Said emulsion method ABS resin II parts by weight are 3～10 parts; Said oxidation inhibitor is selected from phenols, phosphorous acid esters, monothioester kind antioxidant, is used to improve the ABS processing stability.

For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following: a kind of preparation method of ABS resin may further comprise the steps:

A) substance law ABS resin and the emulsion method ABS resin I and the II of aequum and the oxidation inhibitor premix that is selected from phenols, phosphorous acid esters, monothioester class are got compound; Wherein the substance law ABS resin by weight percentage acrylonitrile content be 20～30%; Rubber content is 5～20%, and styrene content is 60～70%; Emulsion method ABS resin I acrylonitrile content by weight percentage is 22～30%, and rubber content 14～25%, styrene content are 50～60%; Emulsion method ABS resin II acrylonitrile content by weight percentage is 7～15%, butadiene content 50～80%, and styrene content is 13～35%;

B) with above-mentioned compound in twin screw extruder, melt extrude, pelletizing, obtain this blended ABS resin after the drying.

In the technique scheme, the extrusion temperature of said twin screw extruder is 200～230 ℃, screw speed 100～150rpm.

In the present invention, substance law ABS and emulsion method ABS blend are extruded, make rubber particles uniform distribution in the SAN matrix of two types.The blended ABS resin impact property of gained is compared amplification with the substance law ABS resin can reach 113%, and other mechanical properties and resistance toheat keep level preferably.Particularly surpass at 50% o'clock at the lower substance law ABS consumption of price, the over-all properties of gained ABS is better, and cost is low, is fit to very much the plastic working enterprise application.

Crazing shear zone theory by ABS resin is toughness reinforcing can know, when receiving the stress that the external world applies, the substance law ABS rubber particles energy-absorbing that particle diameter is bigger also brings out crazing; The emulsion method ABS rubber particles that particle diameter is less can suppress the crazing development, brings out shear zone.When three kinds of particle proportion were suitable, two kinds of effects were brought into play simultaneously, produced the coordination plasticizing effect, and the rubber content increase, made the impact property of resulting ABS improve greatly.

The inventor uses scheme of the present invention to prepare ABS resin, and its raw material is easy to get on market, and cost is relatively low, and the ABS impact property of gained has still kept the excellent comprehensive performance when significantly improving, and has obtained better technical effect.

Through embodiment the present invention is done further elaboration below.

Embodiment

[embodiment 1]

In the present embodiment, substance law ABS (M1) selects the substance law ABS resin of China Petrochemical Industry's Shanghai Gaoqiao Petrochemical Company for use, and wherein acrylonitrile content is 21% by weight percentage, and rubber content is 13%, and styrene content is 66%; The rubber particles volume average particle size is 1.2 μ m, and particle size range is 0.3～2.5 μ m; The Izod notched Izod impact strength is 177J/m, tensile yield strength 37.2MPa, flexural strength 55.0MPa, 82.5 ℃ of heat-drawn wires.Emulsion method ABS (E1), its acrylonitrile content 25%, rubber content 20%, styrene content 55%; The rubber particles volume average particle size is 0.4 μ m, and particle size range is 0.15～3 μ m; Izod shock strength 198J/m, tensile yield strength 47.6MPa, flexural strength 73.8MPa, 82 ℃ of heat-drawn wires.Emulsion method ABS2 (E2) rubber content 70%.Oxidation inhibitor is selected phenolic antioxidant 1010 for use.

Make in the Leistriz AG Mic-27 parallel dual-screw extruding machine M1, E1 and E2 fusion in Germany, mix, extrude, pelletizing.Extrusion temperature is 200～230 ℃.Input speed: 60rpm, screw speed: 110rpm, the raw material residence time in forcing machine is 40～45 seconds.Sample is all following dry 2～4 hours at 80 ℃ before blend is extruded.

Izod notched Izod impact strength measuring method is ASTM D256 among the present invention, and the tensile property measuring method is ISO 527, and the bending property measuring method is ISO 178.The heat-drawn wire measuring method is ASTM D648,1.82MPa load.The melt flow rate(MFR) measuring method is ISO 1133, under 220 ℃, 10kg load, measures.The above-mentioned pellet that makes is cast in the Mechanics Performance Testing batten in injection moulding machine, sample is all following dry 2～4 hours at 80 ℃ before injection moulding.The physicals of sample is as shown in table 1.

The blended ABS performance that table 1 M1 and E1, E2 obtain under the different mixture ratio

Can know by table 1, when M1 and E1 ratio between 80/20～40/60, the shock strength of blended ABS is higher than component M1 and E1 shock strength separately, especially between 70/30～60/40, shock strength can reach 230J/m.Meanwhile, stretching, bending property and resistance toheat are still good.After 10 parts among the E1 replaced with E2, the rubber content of blended ABS increased, and its shock strength also significantly increases, and is 60/30/10 o'clock at the E1/M2/E2 portion rate, and the blended ABS shock strength can reach 338J/m.Especially, be 40/50/10 o'clock at the E1/M1/E2 portion rate, the blended ABS shock strength can reach 361J/m.The stretching of blended ABS, bending and resistance toheat descend to some extent.

[embodiment 2]

Step, condition, testing method by embodiment 1 prepare ABS, just change the substance law ABS that is selected for use.The substance law ABS (M2) that present embodiment is selected for use is also for China Petrochemical Industry's Shanghai Gaoqiao Petrochemical Company ABS resin, acrylonitrile content 22% by weight percentage wherein, rubber content 11%, styrene content 67%; The rubber particles volume average particle size is 0.5 μ m, and particle size range is 0.3～1.1 μ m; The Izod notched Izod impact strength is 164J/m, tensile yield strength 44.5MPa, flexural strength 64.3MPa, 80 ℃ of heat-drawn wires.The physicals of sample is as shown in table 2.

The performance of the blended ABS resin that table 2 M2 and E1, E2 obtain under the different mixture ratio

Can know by table 2; When M2 and E1 ratio between 80/20～50/50; The shock strength of blended ABS keeps and is higher than component M2 and E1 shock strength separately; Can reach 214J/m 70/30 o'clock shock strength, not have the shock strength that the shock strength that does not make blended ABS because of the adding of the lower M2 of shock strength is lower than E1, blended ABS still has good stretching, bending and resistance toheat.After the part of E1 replaced with E2, along with the rubber content of blended ABS increases, its shock strength also significantly increased, and is 60/30/10 o'clock at the E1/M2/E2 portion rate, and the blended ABS shock strength can reach 349J/m.Especially, be 40/50/10 o'clock at the E1/M2/E2 portion rate, the blended ABS shock strength can reach 347J/m, and melt flow rate(MFR), heat-resisting than good with M1.

[embodiment 3]

Step, condition, testing method by embodiment 1 prepare ABS, just change the substance law ABS that is selected for use.The substance law ABS (M3) that present embodiment is selected for use is China Petrochemical Industry's Shanghai Gaoqiao Petrochemical Company ABS resin, its by weight percentage acrylonitrile content be 20%, rubber content is 11%, styrene content is 69%; The rubber particles volume average particle size is 0.5 μ m, and particle size range is 0.3～0.9 μ m; The Izod notched Izod impact strength is 202J/m, tensile yield strength 42.3MPa, 86.5 ℃ of heat-drawn wires.The physicals of sample is as shown in table 3.

The performance of the blended ABS resin that table 3 M3 and E1, E2 obtain under the different mixture ratio

Can know by table 3, when M3 and E1 ratio between 80/20～50/50, the shock strength of blended ABS is higher than component M3 and E1 shock strength separately, can reach 245J/m 70/30 o'clock shock strength.Blended ABS still has good stretching, bending and resistance toheat.After the part of E1 replaced with E2, along with the rubber content of blended ABS increases, its shock strength also significantly increased, and is 60/30/10 o'clock at the E1/M2/E2 portion rate, and the blended ABS shock strength can reach 342J/m.Especially, be 40/50/10 o'clock at the E1/M2/E2 portion rate, the blended ABS shock strength can reach 365J/m, and heat-resisting than good with M1 or M2.

[comparative example 1]

Step, condition, testing method by embodiment 1 prepare ABS resin, are raw material with M3 and E2, M3 and 95/5 blend of E2 ratio of weight and number, and the physicals of gained ABS resin is seen table 4.

[comparative example 2]

Step, condition, testing method by comparative example 1 prepare ABS resin, and just changing the raw materials in part by weight ratio of being selected for use is 85/15, and the physicals of gained ABS resin is seen table 4.

Visible by table 4, the over-all properties of gained ABS does not have of the present invention good.

Table 4 comparative example

Claims (7)

1. ABS resin comprises following component in parts by weight:

A) 10～90 parts of continuous bulk ABS resins, wherein acrylonitrile content is 20～30% by weight percentage, and butadiene content is 5～20%, and styrene content is 60～70%;

B) 10～90 parts of emulsion method ABS resins comprise following component by weight percentage:

(1) 9～89 part of emulsion method ABS resin I, wherein acrylonitrile content is 22～30% by weight percentage, butadiene content 14～25%, styrene content is 50～60%;

(2) 1～10 parts of emulsion method ABS resin II, wherein acrylonitrile content is 7～15% by weight percentage, butadiene content 50～80%, styrene content is 13～35%;

C) 0.01～1 part of oxidation inhibitor.

2. ABS resin according to claim 1; It is characterized in that continuous bulk ABS resin parts by weight are 20～80 parts; Shock strength is at 100～220J/m; The particle size range of rubber particles is 0.1～10 μ m, volume average particle size 0.1～3 μ m, and the weight-average molecular weight of external phase SAN is 130000～180000.

3. ABS resin according to claim 1; It is characterized in that emulsion method ABS resin I parts by weight are 20～80 parts; Shock strength is at 130～500J/m; The particle size range of rubber particles is 0.1～5 μ m, volume average particle size 0.1～1 μ m, and wherein the particle of particle diameter between 0.2～1 μ m accounts for the rubber particles TV more than 60%.

4. ABS resin according to claim 1 is characterized in that emulsion method ABS resin II parts by weight are 3～10 parts.

5. according to the said ABS resin of claim 1, it is characterized in that oxidation inhibitor is selected from phenols, phosphorous acid esters, monothioester kind antioxidant.

6. the preparation method of the said ABS resin of claim 1 may further comprise the steps:

A) substance law ABS resin and the emulsion method ABS resin I and the II of aequum and the oxidation inhibitor premix that is selected from phenols, phosphorous acid esters, monothioester class are got compound; Wherein the substance law ABS resin by weight percentage acrylonitrile content be 20～30%; Rubber content is 5～20%, and styrene content is 60～70%; Emulsion method ABS resin I acrylonitrile content by weight percentage is 22～30%, and rubber content 14～25%, styrene content are 50～60%; Emulsion method ABS resin II acrylonitrile content by weight percentage is 7～15%, butadiene content 50～80%, and styrene content is 13～35%;

B) with above-mentioned compound in twin screw extruder, melt extrude, pelletizing, obtain this blended ABS resin after the drying.

7. according to the preparation method of the said ABS resin of claim 6, it is characterized in that the twin screw extruder extrusion temperature is 200～230 ℃, screw speed 100～150rpm.