CN1375520A - Graft copolymer mixed powder and its characteristic modifying method - Google Patents
Graft copolymer mixed powder and its characteristic modifying method Download PDFInfo
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Abstract
To produce a graft copolymer-based mixed powder that is improved in surface tackiness with high efficiency and is excellent in powder characteristics such as fluidity, or the like, and that is prevented from adhering on a manufacturing device in a manufacturing process, and provide a method for improving powder characteristics of a graft copolymer.The graft copolymer-based mixed powder comprises 100 pts.wt. rubber-containing graft copolymer powder and 0.01-5.0 pts.wt. inorganic fine powder which is subjected to surface treatment with a fatty acid, has an average particle size of not more than 5.0 mu m and an apparent density of not more than 0.35 g/ml and comprises an element selected from the group consisting of Mg, Ca, Ba and Zn. The inorganic fine powder is preferably fine powder of a calcium salt. The fatty acid is preferably a stearic acid. Additionally, silicon dioxide fine powder is preferably incorporated into the mixed powder.
Description
Invention field
The present invention relates to the graft copolymer mixed powder that contains rubber with inorganic micro powder end surface modification, promptly the present invention relates to improve the adhesivity of the graft copolymer powder surface that contains rubber, make the method for modifying of its graft copolymer mixed powder and graft copolymer powder characteristics with good powder characteristics.
Background technology
The hard resin of polyvinyl chloride (PVC) RESINS, polystyrene resin, plexiglass, acrylonitritrile-styrene resin resin etc., be its shock-resistance of improvement with the resin that is called engineering plastics of polycarbonate, PET, PBT, polyacetal etc., the adulterant of the graft copolymer powder that contains rubber is arranged.The graft copolymer powder that contains rubber directly carries out spray-dired method by the latex of emulsion polymerization preparation in hot blast, latex contacts the methods such as method of solidifying and prepares with peptizer such as acid or salt, from gel with its recovery.
But the graft copolymer powder that contains rubber of such method preparation has adhesivity, causes obstruction in storage sometimes.In addition, because adhesivity makes flowability poor, easily cause line of pipes to stop up.Particularly, owing to improve the result of shock-resistance greatly, when the content of the rubbery copolymer in the graft copolymer increases, stop up and make the tendency of line of pipes obturation very high.
In recent years, contain the automatic metering mechanism of graft copolymer powder of rubber or the maximization of line of pipes, when powder easily stops up the situation of mobile difference because the influence that production efficiency reduces increases, so people more and more strong request the characteristic of powder is improved.
Owing to contain the adhesivity of the graft copolymer powder of rubber, from the graft copolymer latex that contains rubber, to reclaim in the process of the graft copolymer powder that contains rubber, each place at fabrication apparatus thereof is adhering to the graft copolymer that contains rubber.Contain graft copolymer one adhesion of rubber, dirt just increases, and effective rate of utilization reduces, because frequent cleaning causes that productivity is low.Particularly,, when carrying out spraying drying, on the inwall of spray-drier, adhere to and pile up, cause various problems as the recovery method of powder.
But for powder characteristics and the adhesivity on the device inner-wall surface of improving the graft copolymer that contains rubber, oriented powder adds the inorganic micro powder end, improves the method for mixed powder surface adhesive.As the inorganic micro powder end, can enumerate various metal oxides, muriate, oxyhydroxide, carbonate, vitriol etc., wherein, consider from the angle that cheaply obtains easily, carry out surface modification with calcium salt.
As such method, the spy opens clear 64-26663 communique, and to propose median size be the method that micropowder below the 10 μ m adds the graft copolymer that contains rubber, in embodiment, put down in writing the example that micropowder uses lime carbonate.
But when adding the micropowder of the special median size of opening clear 64-26663 communique record below 10 μ m, the addition of micropowder must be many, and the modification on surface can not be carried out expeditiously.In addition, the addition of powder increases, and the final performance of the thermoplastic resin of manufacturing reduces.And, because the characteristic of powder can not fully be improved, in manufacturing engineering, just can not prevent that powder from adhering in manufacturing installation.So can not satisfy the present situation in recent years of performance that strong request improves the thermoplastic resin goods of powder and manufacturing.
Summary of the invention
The improving one's methods of powder characteristics that the purpose of this invention is to provide a kind of graft copolymer mixed powder and this graft copolymerization powder, by improving the surface adhesive of this powder, make the powder characteristicss such as flowability of this powder good, prevent that this powder from manufacturing processed, sticking on the manufacturing installation.
Graft copolymer mixed powder of the present invention contains being selected from by containing magnesium, calcium, barium and zinc element of graft copolymer powder 100 mass parts of rubber and 0.01-5.0 mass parts forms inorganic micro powder end in the group, surface treatment is carried out with fat in this inorganic micro powder end, its median size is below 5.0 μ m, and apparent density is below 0.35 grams per milliliter.
In graft copolymer mixed powder of the present invention, above-mentioned inorganic micro powder end preferred calcium salt powder.
In graft copolymer mixed powder of the present invention, the preferred stearic acid of above-mentioned lipid acid.
In graft copolymer mixed powder of the present invention, preferably also contain the fine silica powder end.
The method of modifying of the powder characteristics of the powder of graft copolymer of the present invention, it is characterized in that being selected from by containing magnesium, calcium, barium and zinc element of 0.01-5.0 mass parts formed the inorganic micro powder end of group and joined in graft copolymer powder 100 mass parts that contain rubber, surface treatment is carried out with lipid acid in advance in above-mentioned inorganic micro powder end, its median size is below 5.0 μ m, and apparent density is below 0.35 grams per milliliter.
Below, describe the present invention in detail.
In the present invention, contain the graftomer of rubber, (Tg) makes dry polymeric at the rubbery polymer below 20 ℃ with glass transformation temperature, and polymerisable therein monomer can carry out graft polymerization.Though this material is not particularly limited,, the content of the rubbery polymer in containing the graft copolymer of rubber is more than the 40 weight %, more than the preferred 50 weight %.If the content that contains rubbery polymer in the graft copolymer of rubber is more remarkable with the surface modification effect at inorganic micro powder end more than 50 weight %.
As rubbery polymer, for example, can enumerate polysiloxane series rubber polymer that rubbery polymer, organo-siloxane of being the acrylic acid series of main component with n-butyl acrylate, 2-EHA etc. etc. are main component, divinyl, isoprene, chloroprene etc. is the diene series rubber polymkeric substance of main component.In addition, these rubber polymers preferably use the compounded rubber of two or more combinations.The rubbery polymer that preferably in core, contains glassy polymers.
As employed possible monomer in the graft polymerization of rubbery polymer, vinyl monomer, the ethene that can list aromatic vinyl monomer, cyano groupization is that unsaturated carboxylic acid is that the alkyl ester of monomer, unsaturated carboxylic acid is monomer, halogenated ethene base system monomer, maleic anhydride imide series monomer, can use a kind ofly in these monomers, also can be used in combination.
Be not particularly limited for aforesaid fragrant family monomer, still, for example vinylbenzene, alpha-methyl styrene, methyl-alpha-methyl styrene, Vinyl toluene, Vinylstyrene etc.In these, special optimization styrene.These aromatic vinyl monomers can use one or more to be used in combination.
Have no particular limits for aforesaid cyano group vinyl monomer, still, for example can list vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, α-ethyl acrylonitrile etc.In these, preferred especially vinyl cyanide.These vinyl cyanide base monomers can a kind ofly use, and also can be used in combination.
For aforementioned ethene is that unsaturated carboxylic acid is that monomer is not particularly limited, still, for example can enumerate vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid etc. one, diprotic acid.These ethene are that unsaturated carboxylic acid monomer can a kind ofly use, and also can be used in combination.
Be not particularly limited for aforementioned unsaturated carboxylic acid alkyl ester monomer, but, for example can list methyl acrylate, ethyl propenoate, butyl acrylate, propyl acrylate, 2-EHA, allyl acrylate, glycidyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, propyl methacrylate, this 2-of methacrylic ethylhexyl, allyl methacrylate(AMA), methacrylic ester Racemic glycidol.In the alkyl ester of these unsaturated carboxylic acids, can a kind ofly use, also can be used in combination.
Have no particular limits for halogenated vinyl monomer, but can list vinylchlorid, vinylidene chloride etc.These chlorovinyl monomers can a kind ofly use, and also can be used in combination.
Have no particular limits for the maleic anhydride dant monomer, still, for example can list maleic anhydride imide, normal-butyl maleic anhydride imide, positive cyclohexyl maleic anhydride imide, positive methyl maleic anhydride imide etc.These maleic anhydride dant monomers can a kind ofly use, and also can be used in combination.
And, except that above-mentioned monomer, also can use the possible monomer of emulsion polymerization of ethene, propylene, vinyl-acetic ester, vinyl pyridine etc.
Polymerization process when rubbery polymer and graftomer are prepared is not particularly limited, with common emulsion polymerization method preparation.And the interpolation of the monomer during polymerization, polymerization starter, emulsifying agent can add together, adds continuously, separate that interpolation, multistage add continuously etc.Also these combinations can be carried out.
In addition, the polymerization of rubbery polymer and rubbery polymer preferably separate separately with monomeric graft polymerization and carry out, still, and the preparation of rubbery polymer and the preparation of graftomer, use plural whipping appts, preferably in same whipping appts, carry out continuously.
About polymerization starter, restriction especially still, for example can not used the water-soluble persulfuric acid of Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.; The diisopropyl benzene hydrogen peroxide, to the Meng alkane hydrogen peroxide, cumene hydroperoxide, tertbutyl peroxide, methylcyclohexyl hydrogen peroxide, 1,1,3,3 ,-tetramethyl butyl hydroperoxide, 1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate, t-butyl peroxy-3,5, the organo-peroxide of 5-three-methylhexanoic acid ester etc. is as a kind of redox initiator of composition.
Emulsifying agent is not particularly limited, for example can uses an alkali metal salt of the sulfonic acid of an alkali metal salt of the higher fatty acid of a kind of disproportionation rosin acid, oleic acid, stearic acid etc., a kind of Witco 1298 Soft Acid etc., also they can be used in combination.
As required, except that above-mentioned composition, preferably combination uses linking agent and chain to move agent, and described linking agent is Vinylstyrene, 1-3 divinyl methacrylic ester, allyl methacrylate(AMA), glycidyl methacrylate etc., and it is thio-alcohol, terebene class etc. that described chain moves agent.
The graft copolymer that contains rubber in the present invention preferably reclaims powder with freezing method or spray-drying process.
In this article, so-called freezing method is that latex is contacted with peptizer, the method that the polymkeric substance in the latex is solidified.The latex of the graft copolymer that contains rubber is contacted with peptizer, and described peptizer can list the mineral acid of hydrochloric acid, sulfuric acid, nitric acid etc.; The organic acid of formic acid, acetate etc.; The inorganic salt of calcium chloride, sal epsom, this aluminium of sulphur etc.; The organic acid salt of lime acetate aluminum acetate etc.In general, these peptizer use with the aqueous solution.
The graft copolymer that contains rubber that solidifies can be independent, mixture that also can several polymer latexs.After in the latex that solidifies, adding suitable antioxidant or additive, also can solidify.
In this clotting method, solidification equipment, method, condition are not particularly limited, can be at the interrupter method in the groove, or the continuous processing of in the succeeding vats more than 2, carrying out continuously etc., any method all can be used.
Spray-drying process is with the direct spray-dired method of latex in hot blast.In this spray-drying process, spray drying unit, method, condition etc. are not particularly limited, as long as can will contain the graft copolymer powdered of rubber.For example, as the generation method of latex drop, can be two etc. any method of rotational circle dish-type, pressure nozzle type, double-current nozzle type, the two nozzle types of pressurization.
The latex spraying drying can be carried out separately, also can carry out spraying drying together by several latex mixtures.After in the latex of spraying, adding suitable antioxidant or additive, also can carry out spraying drying.
The capacity of employed drying machine is not particularly limited in spraying drying, from use the small-scale grade use the laboratory, all can use to the drying machine of use at any capacity of the extensive grade of industrial use.
The inorganic micro powder end is the inorganic micro powder end that contains the element that is selected from magnesium, calcium, barium, zinc composition group.For example, can list magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, lime carbonate, barium sulfate, zinc oxide, talcum etc., still, preferred calcium salt.Calcium salt is not particularly limited, wherein preferred lime carbonate.Because lime carbonate is cheap, raise the cost to little amplitude, can make the graft copolymer powder surface modification that contains rubber.
The inorganic micro powder end, median size must be below 5 μ m.Median size is more little, and the surface modification of particle is just good more, and preferred median size is below 1.0 μ m.Median size is a number average bead diameter in the present invention.
Median size for the modification that makes the graft copolymer powder surface that contains rubber reaches satisfied fully degree, must be added excessive inorganic micro powder end greater than 5 μ m.Therefore, improved cost, also influence contains the rerum natura of the graft copolymer of rubber.
The apparent density at inorganic micro powder end must be below 0.35 grams per milliliter, and preferred apparent density is below 0.3 grams per milliliter.The apparent density at inorganic micro powder end because the ratio of the oversize particle in the inorganic micro powder end reduces, can be carried out modification so contain the surface of the graft copolymer powder of rubber expeditiously below 0.35 grams per milliliter.Apparent density surpasses 0.35 grams per milliliter, even for example median size is less than 5 μ m, modification also can not be carried out expeditiously in the surface of containing the graft copolymer powder of rubber.
In the present invention, the apparent density at inorganic micro powder end is the apparent density (settled process) by JIS K5101 pigment test method determination, calculates according to following (1) formula and obtains.
E＝F/V????????(1)
E: apparent density (grams per milliliter)
F: the quality (gram) of handling examination 2 material in the container
V: volume of a container (milliliter)
The inorganic micro powder end is to use lipid acid to carry out surface-treated inorganic micro powder end.Use when not carrying out surface-treated inorganic micro powder end, because its surperficial energy, assemble mutually at the inorganic micro powder end, causes the generation of oversize particle.Because oversize particle can not cover the graft copolymer surface of containing rubber, so the modification efficiency that contains the graft copolymer powder surface of rubber reduces.
Use lipid acid that the calcium salt inorganic micro powder end of using is carried out under the surface-treated situation, the modification that contains the rubber graft copolymer powder surface can be carried out with very high efficient.
Employed lipid acid in the surface treatment at inorganic micro powder end is not limited to aliphatic carboxylic acid especially, for example, can list stearic acid, oleic acid, linolic acid, linolenic acid, eleostearic acid etc.In these acid, preferred stearic acid.Owing to use stearic acid, can prevent the gathering at inorganic micro powder end.
The addition at inorganic micro powder end, graft copolymer 100 mass parts with respect to containing rubber are the 0.01-5.0 mass parts.Be preferably the 0.04-4.0 mass parts.
The addition at inorganic micro powder end is less than 0.01 mass parts, fully modification of surface, and the powder characteristics modification that contains the graft copolymer powder of rubber can not prevent to adhere in manufacturing installation.In addition, surpass 5.0 mass parts, aspect cost and to the rerum natura of the graft copolymer that contains rubber, influence the aspect inequality.
The inorganic micro powder end can be used in combination with SiO 2 powder.Because the fine silica powder end is used in combination with the inorganic micro powder end, can improve the effect of the modification on surface.Particularly, when calcium salt micropowder and SiO 2 powder were used in combination, the effect of surface modification was very high, and what powder adhered in the drying machine prevents that effect is good especially.
The fine silica powder end, if particle diameter below 1 μ m, hydrophobicity, hydrophilic anyly all can use.But particle diameter is preferably below 0.5 μ m.The addition of SiO 2 powder, the graft copolymer resin powder that contains primary elastomeric with respect to 100 mass parts is preferably the 0.005-1.0 mass parts.Be less than 0.005 mass parts, fully modification of surface, the effect of share the fine silica powder end does not fully show; Surpass 1.0 mass parts, the rerum natura of the moulding product transparency etc. can occur influencing.
Graft copolymer mixed powder is to contain the above-mentioned graft copolymer powder of rubber and the material at inorganic micro powder end of containing.The method that the inorganic micro powder end is added the graft copolymer powdered preparation graft copolymer mixed powder that contains rubber is not particularly limited.For example, be added in the dried graft copolymerization powder that contains rubber or in the exsiccant way, add all right.
Contain by freezing method under the situation of powdered of graft copolymer of rubber, the inorganic micro powder end is added in the graft copolymer slurry that contains rubber after solidifying, can mix with the graft copolymerization powder that contains rubber.
Reclaim from latex by spray-drying process under the situation of the graft copolymerization powder that contains rubber, can list the inorganic micro powder end is put in the drying tower of spray-drier continuously, the inorganic micro powder end be added to the method in the graft copolymer that contains rubber.Drop into the inorganic micro powder end when spraying drying continuously, the surface of the graft copolymer that contains rubber that not only finally obtains can modification, and can suppress to contain the adhesion of the graft copolymer of rubber to the drying tower inner-wall surface.
Method in the drying tower is dropped at the inorganic micro powder end continuously, and restriction especially still, for example, from the courtyard portion of drying tower, add in the drying tower by powder feeder from the side, also can suck by the negative pressure in the drying tower.And, by with dry gas, from double flowing nozzle or nozzle such as pressurization double flowing nozzle etc. make the micronized gas of spraying fluid, or the gas that enters cooling disc atomizer mixes and drops in the drying tower continuously.
Like this, graft copolymer mixed powder of the present invention, contain graft copolymer powder 100 mass parts of rubber and the inorganic micro powder end of 0.01-5.0 mass parts because be, surface treatment is carried out with lipid acid in the inorganic micro powder end, median size is below 5.0 μ m, and apparent density is below 0.35 gram/ml, and described inorganic micro powder end is to be selected from the micropowder of being made of the element in the group magnesium, calcium, barium, zinc, does not assemble at the inorganic micro powder end, and the surface that contains the graft copolymer powder of rubber can effectively cover.Therefore, contain the surface modification expeditiously of the graft copolymer powder of rubber, its adhesivity is reduced, the obstruction in the time of can preventing keeping etc.In addition, improved the flowability of the graft copolymer powder that contains rubber, the obstruction in the time of can preventing to carry.
And graft copolymer mixed powder of the present invention can prevent to adhere in manufacturing installation in the manufacturing engineering of powder.Particularly, reclaim in spraying drying under the situation of graft copolymer mixed powder, when in drying tower, existing simultaneously with the graft copolymer latex that contains rubber, by in drying tower, dropping into the inorganic micro powder end continuously, in the drying way, powder particle is carried out surface modification, can prevent to adhere at the drying tower inner-wall surface.So, can reduce pollution, improve the quality of products.Unnecessary frequent cleaning in addition, improves effective rate of utilization, owing to can be boosted productivity.
In addition, graft copolymer mixed powder of the present invention need not increase manufacturing cost significantly, just can carry out modification to the surface of the graft copolymer powder that contains rubber.
By using the stearic acid in the above-mentioned lipid acid, can further improve the efficient of surface modification.
The mixed powder of above-mentioned graft copolymer also contains the fine silica powder end, has further improved the effect with inorganic micro powder end surface modification.Embodiment particularly
Below, according to embodiment the present invention is described." part " in embodiment, the comparative example and " % " be restriction especially not, respectively expression " mass parts " and " quality % ".
Various evaluations in embodiment and the comparative example are pressed the method for showing and are carried out.
Estimate in accordance with the following methods in embodiment and the comparative example in addition.
(1) calcium carbonate powders rerum natura
Median size: measure with electron microscope.
Apparent density: measure according to JIS5101.
(2) block measuring
In cylindrical vessel, add graft copolymer powder 20 grams that contain rubber, preserved 5 hours down in 50 ℃ of temperature 17.5kPa pressure.The block that obtains is measured the broken time (second) of 60% block with micro electromagnetic vibrosieve device (tube well physics and chemistry system) vibration.This time is short more, and anti-obstruction is high more.
(3) powder fluidity graft copolymer powder 50 gram that will contain rubber is being packed in the bulk specific gravity tester of putting down in writing in JIS-K-6721 of vibration-control system, after this, pull down vibration-control system, measure the outflow powder amount (Grams Per Second) that flows out powder in the time per unit.This powder discharge is big more, illustrates that the flowability of this powder is just good more.
Embodiment 1
(1) preparation of rubbery polymer (A-1)
With 2.5 parts of 190 parts of deionized waters, beef fat acid potash soaps, 0.2 part in sodium sulfate, to the Meng 20 parts of alkane hydrogen peroxidase 10 .5 part, 80 parts of 1,3-butadienes and vinylbenzene add in the reaction unit of band whipping appts, begin to stir, be warmed up to 57 ℃ of temperature.
After this, add the mixture of 10 parts of deionized waters, 0.3 part of aqueous crystalline dextrose, 0.2 part of sodium phosphate, 0.003 part of 7 aqueous ferrous sulfate salt in the way of heating up, polymerization begins, and keeps after 8 hours, takes out the rubbery polymer latex (A-1) in the steel basin
(2) contain the preparation of rubbery copolymer latex (A-2)
699 parts in rubbery polymer latex (A-1) (233 parts of solid substances), 85 parts in water, beef fat acid potassium are joined in the reaction unit of being with whipping appts for 3.0 parts, behind nitrogen replacement, add 0.3 part of formaldehyde sodium sulfoxylate dihydrate, interior temperature rise to 70 ℃ temperature.After this, in 30 minutes, add the mixture of 28 parts of methyl methacrylates, 7 parts of ethyl propenoates, 0.15 part of cumene hydroperoxide continuously, kept 100 minutes.After this, in 100 minutes, add the mixture of 55 parts of vinylbenzene, 0.20 part of cumene hydroperoxide continuously, kept 120 minutes.After this, in 30 minutes, add the mixture of 10 parts of methyl methacrylates, 0.05 part of cumene hydroperoxide continuously, keep polymerization in 120 minutes to finish.
The graft copolymer that obtains like this (rubber content 65%) latex, graft copolymer with respect to 100 parts adds 0.21 part of emulsification dispersive triglycol-two [3-(3--シ ャ リ-butyl-5-methyl-4-hydroxy phenyl) propionic ester] and 0.63 part of two dodecyl-3,3 '-thiodipropionate obtains containing the graft copolymer latex (A-2) of rubber.
(3) recovery of polymer powder particle (spraying drying)
It is that 135 ℃, temperature out are that 65 ℃ condition is carried out spraying drying that the graft copolymer latex (A-2) that contains rubber uses nozzle-type spray drying unit (the former chemical industry mechanism in great river), temperature in, obtains powder particle (P-1).
(4) add inorganic micro powder end, powder characteristics evaluation
Adding in 100 parts of the powder particles that obtains (P-1) and carrying out surface-treated apparent density with stearic acid is that 0.24 grams per milliliter, median size are calcium carbonate fine powder end (white lapicide's industry (strain) system of 0.08 μ m, trade(brand)name CCR-B) 0.6 part, mixes obtaining the graft copolymerization powder.This graft copolymerization powder is estimated.The results are shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| Lime carbonate | Surface treatment | Stearic acid | Stearic acid | Stearic acid | Do not have | Stearic acid | Stearic acid |
| Performance density (g/m) | ???0.24 | ??0.23 | ??0.24 | ??0.17 | ??0.40 | ????0.45 | |
| Median size (μ m) | ???0.08 | ??0.20 | ??0.08 | ??0.20 | ??0.08 | ????5.50 | |
| Add umber (part) | ???0.6 | ??0.6 | ??0.6 | ??0.6 | ??0.6 | ????0.6 | |
| The fine silica powder end | Add umber (part) | ???- | ??- | ??0.04 | ??- | ??- | ????- |
| The thermoplastic resin powder | Block (second) | ???21 | ??34 | ??12 | ??380 | ??130 | ????420 |
| Powder fluidity (g/s) | ???2.5 | ??2.1 | ??2.7 | ??1.3 | ??1.6 | ????1.2 |
Embodiment 2
Remove and to use that to carry out the surface-treated apparent density through stearic acid be 0.23 grams per milliliter, median size is the calcium carbonate powders (white lapicide industry (strain) trade(brand)name Vigot-15) of the 0.2 μ m calcium carbonate powders (CCR-B) that replaces the median size 0.08 μ m among the embodiment 1 with outside powder particle (P-1) mixes, other carries out similarly to Example 1, obtains graft copolymer mixed powder.Obtain the graft copolymerization powder evaluating characteristics the results are shown in table 1.
Embodiment 3
Remove 0.04 part at fine silica powder end (Japanese ア エ ロ ジ Le (strain) system trade(brand)name ア エ ロ ジ Le 200FAD) and calcium carbonate fine powder end and add simultaneously, obtain outside the graft copolymer mixed powder, other carries out similarly to Example 1.The evaluation result of the characteristic of this graft copolymer mixed powder is shown in table 1.
Comparative example 1
Removing with not surface treated apparent density is 0.17 grams per milliliter, median size is that to replace median size among the embodiment 1 be that the calcium carbonate fine powder end (CCR-B) of 0.08 μ m is mixed with powder particle (P-1) and obtained outside the graft copolymer mixed powder at the calcium carbonate fine powder end (white lapicide's industry (strain) system trade(brand)name BRT-1500) of 0.2 μ m, and other carries out similarly to Example 1.The evaluation result of the characteristic of this graft copolymer mixed powder is shown in table 1.
Comparative example 2
Remove and to use that to carry out the surface-treated apparent density through stearic acid be 0.4 grams per milliliter, median size is that to replace median size among the embodiment 1 be that the calcium carbonate fine powder end (CCR-B) of 0.08 μ m is mixed with powder particle (P-1) and obtained outside the graft copolymer mixed powder at the calcium carbonate fine powder end (white lapicide's industry (strain) system trade(brand)name CCR) of 0.08 μ m, and other carries out similarly to Example 1.The evaluation result of the characteristic of this graft copolymer mixed powder is shown in table 1.
Comparative example 3
With calcium carbonate powders (white lapicide's industry (strain) trade(brand)name Vigot-15) classification of using among the embodiment 2, obtaining apparent density is 0.45 grams per milliliter, median size is the calcium carbonate fine powder end of 5.5 μ m, replacing median size among the embodiment 1 with this micropowder is that the calcium carbonate fine powder end (CCR-B) of 0.08 μ m is mixed with powder particle (P-1) and obtained outside the graft copolymer mixed powder, and other carries out similarly to Example 1.The evaluation of the characteristic of this graft copolymer mixed powder is shown in table 1.
In embodiment 1 and 2, because what be to use carries out surface treatment with stearic acid, median size is below 5.0 μ m, and apparent density is the following calcium carbonate fine powder end of 0.35 grams per milliliter, so containing the graft copolymer powder of rubber is difficult for stopping up the good fluidity of powder.
In addition, in embodiment 3, owing to further use the fine silica powder end, so contain the more difficult obstruction of graft copolymer powder of rubber.
On the other hand, in comparative example 1, because stearic acid of no use carries out surface treatment to calcium carbonate powders, easily block so contain the graft copolymer powder of rubber, the flowability of powder is poor.
Moreover in comparative example 2, because the apparent density of lime carbonate is more than 0.35 grams per milliliter, the graft copolymer powder that contains rubber easily blocks, and powder fluidity is poor.
In comparative example 3, because the apparent density of lime carbonate is more than 0.35 grams per milliliter, median size is more than the 5.0 μ m, easily blocks so contain the graft copolymer powder of rubber, and powder fluidity is poor.
Embodiment 4
The recovery of polymer powder particle (solidifying)
With respect to 100 parts of the graft copolymer that contains rubber (A-1) solid substances, add 3.0 parts of sulfuric acid, in the container of band whipping appts, be adjusted into 1.2% aqueous sulfuric acid, after this, remain on 40 ℃ of graft copolymer latex solid substances (A-1) that contain rubber that add 100 parts while stirring, in whipping appts, add 2.0 parts methyl methacrylate/butyl acrylate solid substance simultaneously, after this after keeping 5 minutes, the slurry that solidifies slowly is warming up to 85 ℃, obtain slurry and dewater, obtain exsiccant powder particle (P-2).
100 parts of powder particles (P-2) that obtains by freezing method with 0.6 part to carry out the surface-treated apparent density through stearic acid be 0.24 grams per milliliter, median size is that mix at the calcium carbonate fine powder end (white factory's industry (strain) system trade(brand)name CCR-B) of 0.08 μ m, obtains graft copolymer mixed powder.The evaluation of the characteristic of this graft copolymer mixed powder is shown in table 2.
Table 2
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 4 | Comparative example 5 | ||
| Lime carbonate | Surface treatment | Stearic acid | Stearic acid | Stearic acid | Do not have | Stearic acid |
| Performance density (g/m) | ??0.24 | ??0.23 | ????0.24 | ??0.17 | ????0.40 | |
| Median size (μ m) | ??0.08 | ??0.20 | ????0.08 | ??0.20 | ????0.08 | |
| Add umber (part) | ??0.6 | ??0.6 | ????0.3 | ??0.6 | ????0.6 | |
| The thermoplastic resin powder | Block (second) | ??12 | ??21 | ????54 | ??260 | ????82 |
| Powder fluidity (g/s) | ??3.6 | ??3.5 | ????3.4 | ??2.2 | ????2.5 |
Embodiment 5
Remove and to use that to carry out the surface-treated apparent density through stearic acid be 0.23 grams per milliliter, median size be the calcium carbonate fine powder end (white lapicide's industry (strain) system trade(brand)name Vigot-15) of 0.2 μ m replace median size among the embodiment 4 be the calcium carbonate fine powder end (CCR-B) of 0.08 μ m with outside powder particle (P-2) mixes, other carries out similarly to Example 4.The evaluation of the characteristic of this graft copolymer mixed powder is shown in table 2.
Embodiment 6
Remove 100 parts of relative powder particles (P-2), the calcium carbonate fine powder end of adding 0.3 part obtains outside the graft copolymer mixed powder, and other carries out similarly to Example 4.The evaluation of the characteristic of this graft copolymer mixed powder is shown in table 2.
Comparative example 4
Except that carrying out the surface-treated apparent density is 0.17 grams per milliliter, median size is calcium carbonate fine powder end (white lapicide's industry (strain) system of 0.2 μ m, trade(brand)name BRT-1500) replacing median size among the embodiment 4 is that the calcium carbonate fine powder end (CCR-B) of 0.08 μ m is mixed with powder particle (P-2) and obtained outside the graft copolymer mixed powder, and other carries out similarly to Example 4.The evaluation result of the characteristic of this graft copolymer mixed powder is shown in table 2.
Comparative example 5
Remove and to use that to carry out the surface-treated apparent density through stearic acid be 0.4 grams per milliliter, median size is that to replace median size among the embodiment 4 be that the calcium carbonate fine powder end (CCR-B) of 0.08 μ m is mixed with powder particle (P-2) and obtained outside the graft copolymer mixed powder at the calcium carbonate fine powder end (white lapicide's industry (strain) system trade(brand)name CCR) of 0.08 μ m, and other carries out similarly to Example 4.The evaluation result of the characteristic of this graft copolymer mixed powder is shown in 2.
In embodiment 4-6, owing to use stearic acid to carry out surface treatment, median size is below 5.0 μ, and apparent density is the following lime carbonate of 0.35 grams per milliliter, so the graft copolymer that contains rubber is difficult for blocking, powder fluidity is good.
On the one hand, in comparative example 4, because stearic acid of no use carries out surface treatment to calcium carbonate powders, so the graft copolymerization powder that contains rubber is easy to block, powder fluidity is poor.
Moreover in comparative example 5, because the apparent density of calcium carbonate powders is more than 0.35 grams per milliliter, so the graft copolymerization powder that contains rubber is easy to block, powder fluidity is poor.
Embodiment 7
(1) contains the preparation of the graft copolymer latex (A-3) of rubber
With 2 parts of tetraethoxysilanes, 0.5 part of gamma-methyl allyl acyloxypropyl dimethoxy methyl-monosilane, 97.5 parts of mixing of octamethylcyclotetrasiloxane, obtain 100 parts of mixture of siloxanes.
After this, 100 parts of addings of this mixture of siloxanes have been dissolved in 200 parts of the deionized waters of each 1 part Sodium dodecylbenzene sulfonate and Witco 1298 Soft Acid.With homogenizer with 10000 rev/mins of preliminary stirrings after, divide diffusingly in the pressure lactogenesis of 30Mpa with the homogenizing pump, obtain organo-siloxane latex.With this organo-siloxane latex steel basin of packing into, begin to stir, 80 ℃ keep 5 hours after, placed 48 hours at 20 ℃.After this, with adjusting to 7.4 in the aqueous sodium hydroxide solution and with the pH of this latex, after polymerization finishes, in steel basin, take out organopolysiloxane rubbery polymer latex.
33 parts of the elastomeric polymer latexs of the organopolysiloxane that obtains (10 parts of rubbery polymers) are packed into be with in the reaction unit of whipping appts, to wherein adding 1.4 parts of polyoxyethylene alkyl phenyl ether sulfuric esters (flower king's (strain) エ マ one Le NC-35), 271 parts of deionized waters.After this, behind nitrogen replacement, be warming up to 50 ℃, add the mixed solution of 0.40 part of 78.4 parts of n-butyl acrylates, 1.6 parts of allyl methacrylate(AMA)s and tertbutyl peroxide, stirred 30 minutes.After this, add the mixed solution of 5 parts of 0.002 part in ferrous sulfate, 0.006 part of disodium edta, 0.26 part of formaldehyde sodium sulfoxylate dihydrate and deionized waters, beginning radical polymerization.After this, in 70 ℃, kept 2 hours, then in 15 minutes, drips the mixture of 0.05 part of tertbutyl peroxide and 10 parts of methyl methacrylates in 70 ℃ of temperature.After this, after 4 hours, in steel basin, take out the graft copolymer latex (A-3) that contains rubber 70 ℃ of maintenances.
(2) recovery of polymer powder particle
Use the spray-drier among the embodiment 1, spraying drying contains the graft copolymer latex (A-3) of rubber under 30 kilograms of solid substances/hour condition, simultaneously, the charging opening of the vertical tube part by spray-drier, carrying out the surface-treated apparent density by the continuous interpolation of 0.3 kilogram/hour condition with stearic acid is 0.24 grams per milliliter, median size be 0.08 μ m calcium carbonate powders (white lapicide's industry (strain) system, CCR-B).Behind the continuous operation 1 hour, confirm the adhesion situation of drying machine inner-wall surface place powder, following evaluation powder is in the adhesion situation of drying machine inner-wall surface.Its result is as shown in table 3.
◎ does not adhere to
Zero adheres to seldom
● adhere to very many
Table 3
Embodiment 8
| Embodiment 7 | Embodiment 8 | Comparative example 6 | |
| Adhesion situation in the drying machine | ????○ | ????◎ | ?????● |
Remove when carrying out spraying drying, (outside (Japanese ア エ ロ ジ Le (strain) system trade(brand)name ア エ ロ ジ Le R972), other carries out similarly to Example 7 to add the fine silica powder end by 0.015 kilogram of/hour condition in drying tower in the time of with the interpolation calcium carbonate powders.Powder is as shown in table 3 in the adhesion situation of drying machine inner-wall surface.
Comparative example 6
Except that not adding the calcium carbonate fine powder end in drying tower, other carries out similarly to Example 7.The results are shown in table 3.
In embodiment 7, to carry out the surface-treated apparent density through stearic acid be 0.24 grams per milliliter owing to use simultaneously, and median size is the calcium carbonate powders of 0.08 μ m, and the graft copolymer that contains rubber does not adhere in drying machine.
In embodiment 8,, in drying machine, more do not adhere to so contain the graft copolymer of rubber owing to also use the fine silica powder end.
On the one hand, in comparative example 6,, in drying machine, adhere to very many so contain the graft copolymer of rubber owing to do not add the calcium carbonate fine powder end.
As mentioned above,, use specific cheap inorganic micro powder end, just can carry out surface modification the graft copolymer powder that contains rubber according to the present invention.Therefore, need not increase substantially cost, block during powder conveying, the obstruction during automatic gauge can eliminate, preparation facilities also can correspondingly maximize.
Claims (5)
1. graft copolymer mixed powder, it is characterized in that containing graft copolymerization powder 100 mass parts and the inorganic micro powder end 0.01-5.0 mass parts of rubber, surface treatment is carried out with lipid acid in described inorganic micro powder end, its median size is below 5.0 μ m, and apparent density is below 0.35 grams per milliliter; Described inorganic micro powder end is to be selected from by containing magnesium, calcium, barium, zinc to form the inorganic micro powder end of the element in the group.
2. the graft copolymerization powder of putting down in writing by claim 1 is characterized in that described inorganic micro powder end is a calcium salt.
3. the graft copolymerization powder of being put down in writing by claim 1 or 2 is characterized in that described lipid acid is stearic acid.
4. by each graft copolymerization powder of putting down in writing of claim 1-3, it is characterized in that also containing the fine silica powder end.
5. the method for modifying of a graft copolymer powder characteristics, it is characterized in that in the graft copolymerization powder that contains rubber of 100 mass parts, add the inorganic micro powder end of 0.01-5.0 mass parts, handle with lipid acid at above-mentioned inorganic micro powder end, its median size is below 5.0 μ m, and apparent density is below 0.35 grams per milliliter; Described inorganic micro powder end is to be selected from by containing magnesium, calcium, barium, zinc to form the inorganic micro powder end of the element in the group.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001074533A JP4961078B2 (en) | 2001-03-15 | 2001-03-15 | Graft copolymer mixed powder and method for improving powder properties of graft copolymer |
| JP2001074533 | 2001-03-15 |
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| CN1375520A true CN1375520A (en) | 2002-10-23 |
| CN1229432C CN1229432C (en) | 2005-11-30 |
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Cited By (1)
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|---|---|---|---|---|
| CN101671494B (en) * | 2009-09-19 | 2013-03-20 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005017026A1 (en) * | 2003-08-14 | 2005-02-24 | Mitsubishi Rayon Co., Ltd. | Material containing rubbery polymer, process for producing the same, and thermoplastic resin containing the same |
| JP7044617B2 (en) * | 2018-04-23 | 2022-03-30 | 株式会社クラレ | Manufacturing method of thermoplastic resin powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6426663A (en) * | 1987-04-13 | 1989-01-27 | Kanegafuchi Chemical Ind | Method for improving powder characteristic of synthetic polymer powder |
| JP3110526B2 (en) * | 1991-11-08 | 2000-11-20 | 水澤化学工業株式会社 | Hydrotalcite-coated particles, production method thereof and compounding agent for resin |
| JPH06157923A (en) * | 1992-08-31 | 1994-06-07 | Mitsubishi Rayon Co Ltd | Production of thermoplastic polymer powder |
| JPH07268017A (en) * | 1994-03-31 | 1995-10-17 | Mitsubishi Rayon Co Ltd | Production of thermoplastic polymer powder |
| JP3151196B2 (en) * | 1998-04-10 | 2001-04-03 | 丸尾カルシウム株式会社 | Surface-treated calcium carbonate filler, method for producing the same, and resin composition containing the filler |
| JP2001049225A (en) * | 1999-06-02 | 2001-02-20 | Sekisui Chem Co Ltd | Moisture-curing urethane adhesive composition and sealing composition |
| JP2001170984A (en) * | 1999-12-17 | 2001-06-26 | Hitachi Chem Co Ltd | Method for producing thermoplastic resin sheet |
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| CN101671494B (en) * | 2009-09-19 | 2013-03-20 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
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| JP2002265743A (en) | 2002-09-18 |
| JP4961078B2 (en) | 2012-06-27 |
| CN1229432C (en) | 2005-11-30 |
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