CN102030965A - ABS material with high color fastness and preparation method thereof - Google Patents

Abstract

The invention discloses an acrylonitrile butadiene styrene (ABS) material with high color fastness and a preparation method thereof. The ABS material consists of the following components in part by weight: 100 parts of acrylonitrile-butadiene-styrene copolymer, 5 to 25 parts of acrylonitrile-N-benzyl-maleimide-maleic-anhydride terpolymer, 2 to 8 parts of compatilizer, 0.5 to 4 parts of talcpowder, and 0.2 to 5 parts of processing aid. By blending the -N-benzyl-maleimide copolymer and the acrylonitrile-butadiene-styrene copolymer base body, the ABS material has better consistency and mechanical property, the defect of insufficient color fastness of a product prepared from the ABS material under severe environment conditions of high temperature, boiling, illumination and the like is overcome, the application field of the ABS material is expanded and the service life of the product is prolonged; meanwhile, the preparation method is easy and has a good application prospect.

Description

A kind of high color fastness ABS material and preparation method thereof

Technical field

The present invention relates to polymeric material field, relate in particular to a kind of high color fastness ABS material and preparation method thereof.

Background technology

ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-styrene-butadienecopolymer) resin is a kind of intensity height, good toughness, be easy to thermoplastics type's macromolecular material of machine-shaping.ABS resin is because of showing the synergisticing performance of three kinds of components, so have excellent properties such as surface hardness height, low-temperature impact resistance is good, dimensional stability is good, molding shrinkage is little, processing characteristics is good, be widely used in fields such as household appliances, electric appliance casing, automotive material.But, because ABS resin has limited its application in some high requirement field in the defective that configuration aspects exists.

There are bigger difference in vinyl cyanide, divinyl, vinylbenzene three content in the ABS resin in the product of different synthetic producers, and this difference to the different three's ratio of toner affinity directly causes the affinity difference of ABS resin to toner.In the ABS resin because the existence of divinyl component, molecular chain is comparatively soft, molecular chain twines loose, and owing to lack very large space sterically hindered group in the molecular chain, cause the molecular chain ratio to be easier to slippage under hot conditions, finally make toner from ABS resin, separate out easily; In addition, the divinyl component that contains in the molecule of ABS resin is aging under the effect of light and heat easily, molecular rupture, degraded, thus ABS resin intensity and toughness are descended significantly, also flavescence of color, change ash, deepening, surface gloss descend, and have influenced the use of the finished product.For some product, need in rugged environments such as high temperature, poach, illumination, use for a long time, as soybean milk maker shell, meter case, game host shell etc., product is aging easily, the deficiency of resin colour fastness, make easily that the finished product fade, the disadvantageous variation of degradation under the variable color, glossiness, limited the use of ABS resin in these fields.

Summary of the invention

The invention provides a kind of high color fastness ABS material and preparation method thereof, the product that uses this ABS material to make can use in rugged environments such as high temperature, poach, illumination for a long time, has enlarged the use range of ABS material.

Technical scheme of the present invention is: a kind of high color fastness ABS material, composed of the following components by weight:

Acrylonitrile-butadiene-styrene copolymer 100

Vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer 5～25

Compatilizer 2～8

Talcum powder 0.5～4

Processing aid 0.2～5.

A kind of aforesaid high color fastness ABS preparation methods comprises:

Step 1, earlier with acrylonitrile-butadiene-styrene copolymer, vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, compatilizer, talcum powder respectively in vacuum drying oven, dry 4h～6h under 85 ℃～100 ℃ conditions;

Step 2, processing aid and dried acrylonitrile-butadiene-styrene copolymer, vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, compatilizer, talcum powder joined mix 5min～10min in the high-speed mixer;

Step 3, the material that step 2 is mixed join in the twin screw extruder hopper, through fusion, extrude; The fabrication process condition of twin screw extruder is: 170 ℃～200 ℃ of district's temperature, 180 ℃～220 ℃ of two district's temperature, 190 ℃～240 ℃ of three district's temperature, 190 ℃～240 ℃ of four district's temperature, 190 ℃～240 ℃ of five district's temperature, 190 ℃～240 ℃ of six district's temperature, 190 ℃～240 ℃ of head temperatures; Residence time 1min～3min, pressure are 12Mpa～18MPa;

Step 4, material bar that twin screw extruder is extruded are dried 3h～5h through water-bath cooling back pelletizing.

The present invention uses the multipolymer of N-phenylmaleimide, have better consistency and mechanical property with the blend of acrylonitrile-butadiene-styrene copolymer matrix, improved product colour fastness defect of insufficient under harsh environmental conditions such as high temperature, poach, illumination that the ABS material makes, enlarged the Application Areas of ABS material, prolonged the work-ing life of product product, and the preparation method is simple, has a good application prospect.

Embodiment

High color fastness ABS material of the present invention, composed of the following components by weight:

Acrylonitrile-butadiene-styrene copolymer 100

Vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer 5～25

Compatilizer 2～8

Talcum powder 0.5～4

Processing aid 0.2～5.

Further, in the described acrylonitrile-butadiene-styrene copolymer, promptly the divinyl weight percentage in the ABS resin is 5%～30%, and the vinylbenzene weight percentage is 40%～70%, and the vinyl cyanide weight percentage is 10%～30%.

Further, in described vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, the N-phenylmaleimide weight percentage is 45%～65%, and second-order transition temperature is 200 ℃～220 ℃, and 5% thermal weight loss temperature is higher than 360 ℃.

Further, described compatilizer is a styrene-grafted maleic anhydride copolymer, and the maleic anhydride weight percentage is 8%～25%.

Further, described talcum powder is handled through pre-activated, granularity is 1250 orders～5000 orders, activation pretreatment is: under 75 ℃～125 ℃ conditions of temperature, after adding silane series coupling agent, mixed in high speed agitator 2～4 hours, the rotating speed of homogenizer is 1500～4500 rev/mins.

Further, described processing aid comprises oxidation inhibitor, thermo-stabilizer, anti-UV agent, lubricant and releasing agent.

Further, described oxidation inhibitor is suffocated amine antioxidant, such as four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester; Described thermo-stabilizer is a triphenyl phosphite; Described anti-UV agent is UV light absorber such as benzophenone series; Described lubricant is the modification ethylene bis stearic amide; Described releasing agent is an organopolysiloxane.

The present invention makes the principle process of ABS material under the brief description:

In order to stop toner to be separated out from resin, the present invention carries out modification to resin matrix, and high stiff molecule chain increases the mobile difficulty of dislocation and the rotation steric hindrance of molecular chain in the resin thereby increase, thereby separate out on the top layer that makes toner be difficult to move to resin.More effective way is that ABS resin and resin or auxiliary agent with this molecular structure are carried out blending and modifying, and the resin that is fit to this condition has styrene-grafted maleic anhydride (PS-g-MAH), aromatic copolycarbonate (PC), N-phenylmaleimide (N-PMI) and modification kind thereof, polyphenylene sulfide (PPS).Consider the cost factor in the actual mechanical process of this blending and modifying, the validity of modified structure, the factors such as process window of modifying process, can select N-PMI and modification kind and PC.But, after ABS and the PC blend, because the adding of PC, the processing viscosity of resin sharply descends, processing temperature increases substantially, and the existence of PC causes inevitable some unrelieved stresss of existence more or less after the resin treatment, makes the phenomenon that may occur stress cracking in the use of product, has potential safety hazard.Therefore, the present invention selects to add the mode of N-PMI or its modification kind resin, increases moving of molecular chain in sterically hindered, the restriction ABS resin of molecular chain in the ABS resin, thereby improves colour fastness.Simultaneously, this modification has also obtained the effect of the ABS resin of high heat distortion temperature, high mechanical strength, its product is boiled as the hot water bubble in high temperature can not occur the problem of softening, being out of shape in the process.

For N-PMI, because it contains sterically hindered bigger imide group, limited rotation, distortion, the slippage of molecular chain, can very effective lifting and the second-order transition temperature of the ABS resin of its blend.In order to promote the consistency of N-PMI and ABS resin, can be with itself and suitable monomers copolymerization, as introduce strong polar maleic anhydride (MAH) group, glycidyl methacrylate (GMA) group etc., as introducing the vinylbenzene identical or similar, vinyl cyanide, butadiene-styrene group etc. with the ABS structure.The product that preferred in the present invention N-PMI and vinyl cyanide, maleic anhydride terpolymer obtain.

Vinyl cyanide-N-phenylmaleimide of the present invention-maleic anhydride terpolymer, comparatively suitable preparation method is to use that polar monomer causes, solution copolymerization, and suitable trigger monomer can list as azo-compound, acyl peroxide, alkyl peroxide, peroxyester, hydroperoxide, peroxy dicarbonate, ketone peroxide, mineral-type superoxide.In above initiator, the initiator of the preferred peroxyesters of the present invention, persulfuric acid salt, further preferred use contains two free radicals, makes polyreaction that the peroxidation terephthalic acid di tert butyl carbonate of high conversion efficiency be arranged.

This vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, along with the wherein increase of N-PMI content, the second-order transition temperature of multipolymer, mechanical strength and rigidity, 5% thermal weight loss temperature also improve thereupon, than the modified resin of independent use N-PMI, have better consistency, can access better properties and effect as ABS resin.Preferably, the N-phenylmaleimide weight percentage is 45%～65%, and second-order transition temperature is 200 ℃～220 ℃, and 5% thermal weight loss temperature is higher than 360 ℃.

In order to make inorganic toner and ABS resin matrix that good consistency, affinity be arranged, can be by adding the talcum powder that has good compatible ability with the ABS resin matrix.This talcum powder is through surface treatment, with coupling agent to have one section of a polar affine, and the other end of coupling agent and whole molecular chain skeleton are organic composition, thereby have good sticking power with ABS resin.Simultaneously, because talcous laminar structured feature, talcum powder has the lubricated effect of certain increase, for the dispersiveness that increases toner, make the homodisperse of toner in ABS resin also have certain promotion to rent.

For aforesaid talcum powder preprocessing process, concrete is: under higher temperature, will dilute good coupling agent, be that coupling agent such as coupling agent carries out surface activation process to talcum powder as silane series coupling agent, titanic acid ester.As this silane series coupling agent, can optimize the silane coupling agent that end group is an epoxide group, also can select end group in addition for use is amino silane coupling agent, also can select the mixture of two kinds of coupling agents for use.Mandatory declaration be, in the present invention, end group be epoxy group or amino silane coupling agent aspect talcous surface-activation effect, be very nearly the same, different is, it is that the silane coupling agent of epoxide group is more high temperature resistant that end group is compared end group for amino silane coupling agent.Silane series coupling agent and titanic acid ester are that coupling agent is aspect the effect of talcous surface activation process, show as the mechanical property of the finished product variant slightly, the rigidity of the glass fiber reinforced polycarbonate material that obtains after the silane coupling agent activation treatment has obtained raising to a certain degree, and the result of titante coupling agent then is that impelling strength has improvement to a certain degree.

For the process of activation treatment, the preferred condition of the present invention is: under 75 ℃～125 ℃ the temperature condition, add an amount of silane series coupling agent after, (rotating speed is 1500～4500 rev/mins) mixed 2～4 hours in high speed agitator; Talcum powder after treatment, the surface is nonpolar state, has good consistency with the engineering plastic resin matrix.

Such silane series coupling agent, on the market a lot of selections can arranged, as, can select domestic KH-550, KH-560, KH-570, external A-1100, A-187, A-174, KR-TTS, KR-138 (U.S. combinating carbide company), Z-6011, SH-6030 (Dow corning chemical company), KBM-903, KBM-403, KBM-503 (Japanese Shin-Etsu Chemial Co., Ltd) etc.

Between base-material and auxiliary agent involved among the present invention, the insufficient problem of some consistencies of existence more or less, can not melt, cause its molecule interchain to twine not enough, excessive clearance fully altogether with modified additive wherein as ABS resin, " absorption " scarce capacity of toner composition and interlaminar resin, anti-UV agent, oxidation inhibitor are subjected to thermal process to precipitate into reasons such as material surface easily, must use necessary means to improve the consistency of inner each material component of resin.Consider that this material modified base material is an ABS resin, suitable method is that adding a kind of is the compatilizer of base material with ABS or the material close with the ABS component structure, as polystyrene graft maleic anhydride (PS-g-MAH), ABS grafted maleic anhydride (ABS-g-MAH), ABS graft glycidyl methacrylate (ABS-g-GMA), hydrogenated styrene-butadienecopolymer grafted maleic anhydride (SEBS-g-MAH), hydrogenated styrene-butadienecopolymer graft glycidyl methacrylate (SEBS-g-GMA) etc.Wherein, preferred compatible auxiliary agent is PS-g-MAH or ABS-g-MAH, and further preferred compatilizer is PS-g-MAH, and maleic anhydride content is 8%～25%.

The ABS material of a kind of high color fastness of the present invention, because it is positioned to use in the environment that bears conditions such as high temperature, outdoor light at needs, and consider the needs of material modification production, machine-shaping process, need to add thermo-stabilizer, antioxidant, anti-UV agent, releasing agent, lubricant etc.

It is thermo-stabilizer that thermo-stabilizer can select phosphorus, can list phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester etc., concrete can enumerate triphenyl phosphite, Wytox 312, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite decyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl monophenyl, triethyl phosphate, dibutyl phosphate etc.Wherein, preferred Wytox 312, distearyl pentaerythritol diphosphites.

These thermo-stabilizers can use separately, perhaps composite use more than 2 kinds, the use addition of this thermo-stabilizer, 100 weight parts with respect to the ABS resin matrix, be preferably 0.0001～1 weight part, more preferably 0.0005～0.5 weight part, more preferably 0.002～0.3 weight part.

As oxidation inhibitor, can list the trade mark and be 1010,1076, DLTDP, DSTDP, 245, BHT, 1098 oxidation inhibitor.

As anti-UV agent, can list 2,2 '-dihydroxyl-4-methoxy benzophenone is the benzophenone series UV light absorber of representative, and for example with 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl) 5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene radical two, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-2H-benzotriazole and 2-(3,5-two tert-pentyls-2-hydroxy phenyl) benzotriazole are that the benzotriazole of representative is a UV light absorber; And also can use with two (2,2,6,6-tetramethyl--4-piperidyl) sebates, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate etc. is photostabilizer for the hindered amine of representative; Further, also can use 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol, 2-(4,6-3,5-dimethylphenyl-1,3,5-triazines-2-yl)-hydroxyphenyltriazinuv based compounds such as 5-hexyloxy phenol.The use level of these anti-UV agent, photostabilizer, 100 weight parts with respect to the ABS resin matrix are preferably 0.01～2 weight part.

Demolding performace when further improving melt molding, the present invention can also be added in the scope of not destroying the object of the invention collocation and use releasing agent.As releasing agent, can list high-grade aliphatic ester, paraffin, beeswax of alkene wax, silicone oil, organopolysiloxane, monobasic or polyvalent alcohol etc., the usage quantity of this releasing agent with respect to 100 weight parts of ABS resin matrix, is preferably 0.01～2 weight part.

For a kind of high color fastness ABS preparation methods described in the present invention, the ABS raw material that is used, relevant auxiliary agent etc. can be mixed, by melt blending in twin screw extruder.The present invention preferably uses the exhaust twin screw extruder to carry out melting mixing.

For a kind of high color fastness ABS material described in the present invention, the performance characterization mode is divided into the mechanical property sign and colour fastness characterizes.In case study on implementation of the present invention, the test of mechanical property and sign are all according to ISO relevant criterion (International Standards Organization International Standards Organization); Test condition is 23 ℃, 53% relative humidity.

Tensile strength/elongation at break: ISO 527; Flexural strength/modulus in flexure: ISO 178; Socle girder notched Izod impact strength: ISO 179; Heat-drawn wire: ISO 75 (under the 1.82Mpa condition);

The characteristic manner of colour fastness can be boiled certain hour by the contrast standard colour table in boiling water (100 ℃) after, with the total color difference value Δ E of colour table according to CIE standard (Commissionm Internationale de I ' Eclairage, the French title of international lighting association) test colour-change.

In following embodiment 1 to 9, ABS can select ABS-1 for use: the PA-757 of Taiwan strange beautiful (CHIMEI Co.), 3504 of ABS-2:DOW, ABS-3: the HI-121H of Korea S LG; Heat-resistant agent is vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, the N-PMI content 45% of heat-resistant agent 1, the content 2% of maleic anhydride, vinyl cyanide 53%, the N-PMI content of heat-resistant agent 2 is 56%, the content 2% of maleic anhydride, vinyl cyanide 42%, and the N-PMI content of heat-resistant agent 3 is 65%, the content 2% of maleic anhydride, vinyl cyanide 33%; SMA is a styrene-grafted maleic anhydride compatilizer, SMA-1: percentage of grafting 18%, the SMA 218 that can select for use Shanghai research institute of China Petrochemical Industry to produce; SMA-2: percentage of grafting 25%, the SMA M25 that can select for use Shanghai research institute of China Petrochemical Industry to produce.Oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, selects for use Ciba company to produce, and trade names are respectively Irganox1010.Silane coupling agent select for use the SH-6030 of Dow corning or Japanese SHIN-ETSU HANTOTAI KBM-503 both one of.

Following table 1 and table 2 are the composition weight umber of embodiments of the invention 1 to 9 and Comparative Examples 1 to 3 and the performance test data of ABS material.

Table 1

Table 2

Can know by above embodiment 1 to 9, increase along with vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer and styrene-grafted maleic anhydride content, the mechanical strength of gained ABS material, increase as tensile strength, flexural strength, the lifting that heat-drawn wire is also apparent in view, aberration variation through material after the poach has also reduced, but, no small decline has also appearred in the toughness index shock strength of material, finally will influence material in the use that needs aspects such as tapping, injection moulding buckle structure.

Analyzing above embodiment 1 to 9 can know, when the adding proportion of each component in embodiment 4～6 these scopes, can make every performance relatively more balanced, have a water boiling resistance, material modified preferably than the ABS of high color fastness; And as high color fastness ABS material of the present invention, can be in the proportional range of each component that the present invention mentions, according to the actual use field of this material, concrete application requiring and adjust the ratio of each component.

More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (8)

1. a high color fastness ABS material is characterized in that, and is composed of the following components by weight:

Acrylonitrile-butadiene-styrene copolymer 100

Vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer 5～25

Compatilizer 2～8

Talcum powder 0.5～4

Processing aid 0.2～5.

2. high color fastness ABS material according to claim 1 is characterized in that:

In the described acrylonitrile-butadiene-styrene copolymer, the divinyl weight percentage is 5%～30%, and the vinylbenzene weight percentage is 40%～70%, and the vinyl cyanide weight percentage is 10%～30%.

3. high color fastness ABS material according to claim 1 is characterized in that:

In described vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, the N-phenylmaleimide weight percentage is 45%～65%, and second-order transition temperature is 200 ℃～220 ℃, and 5% thermal weight loss temperature is higher than 360 ℃.

4. high color fastness ABS material according to claim 1 is characterized in that:

Described compatilizer is the copolymer of styrene-grafted maleic anhydride, and the maleic anhydride weight percentage is 8%～25%.

5. high color fastness ABS material according to claim 1 is characterized in that:

Described talcum powder is handled through pre-activated, granularity is 1250 orders～5000 orders, and activation pretreatment is: under 75 ℃～125 ℃ conditions of temperature, behind the adding silane series coupling agent, mixed in high speed agitator 2～4 hours, the rotating speed of homogenizer is 1500～4500 rev/mins.

6. high color fastness ABS material according to claim 1 is characterized in that:

Described processing aid comprises oxidation inhibitor, thermo-stabilizer, anti-UV agent, lubricant and releasing agent.

7. high color fastness ABS material according to claim 6 is characterized in that:

Described oxidation inhibitor is suffocated amine antioxidant; Described thermo-stabilizer is a triphenyl phosphite; Described anti-UV agent is the benzophenone series UV light absorber; Described lubricant is the modification ethylene bis stearic amide; Described releasing agent is an organopolysiloxane.

8. one kind as the described high color fastness ABS of the arbitrary claim of claim 1 to 7 preparation methods, it is characterized in that, comprising:

Step 1, earlier with acrylonitrile-butadiene-styrene copolymer, vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, compatilizer, talcum powder respectively in vacuum drying oven, dry 4h～6h under 85 ℃～100 ℃ conditions;

Step 2, processing aid and dried acrylonitrile-butadiene-styrene copolymer, vinyl cyanide-N-phenylmaleimide-maleic anhydride terpolymer, compatilizer, talcum powder joined mix 5min～10min in the high-speed mixer;

Step 3, the material that step 2 is mixed join in the twin screw extruder hopper, through fusion, extrude; The fabrication process condition of twin screw extruder is: 170 ℃～200 ℃ of district's temperature, 180 ℃～220 ℃ of two district's temperature, 190 ℃～240 ℃ of three district's temperature, 190 ℃～240 ℃ of four district's temperature, 190 ℃～240 ℃ of five district's temperature, 190 ℃～240 ℃ of six district's temperature, 190 ℃～240 ℃ of head temperatures; Residence time 1min～3min, pressure are 12Mpa～18MPa;

Step 4, material bar that twin screw extruder is extruded are dried 3h～5h through water-bath cooling back pelletizing.