CA1102461A - Process for preparing compounding ingredients for vinyl chloride resins - Google Patents
Process for preparing compounding ingredients for vinyl chloride resinsInfo
- Publication number
- CA1102461A CA1102461A CA273,912A CA273912A CA1102461A CA 1102461 A CA1102461 A CA 1102461A CA 273912 A CA273912 A CA 273912A CA 1102461 A CA1102461 A CA 1102461A
- Authority
- CA
- Canada
- Prior art keywords
- additive
- tacky
- maleate
- compounding
- dibutyltin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for producing a compounding ingredient for vinyl chloride resins by compounding a liquid or tacky additive into a powder of emulsion-polymerized polyvinyl chloride under heating, whereby a granulated and non-tacky compounding ingred-ient having a high content of the additive is obtained.
A process for producing a compounding ingredient for vinyl chloride resins by compounding a liquid or tacky additive into a powder of emulsion-polymerized polyvinyl chloride under heating, whereby a granulated and non-tacky compounding ingred-ient having a high content of the additive is obtained.
Description
6~
1. Field of the Invention The present invention relates to a process for preparing a compounding ingredient for vinyl chloride resins and, more particularly, it relates to a process for preparing a granulated compounding ingredient for vinyl chloxide resins by compounding a liquid or tacky additive into emulsion-polymerized polyvinyl chloride.
1. Field of the Invention The present invention relates to a process for preparing a compounding ingredient for vinyl chloride resins and, more particularly, it relates to a process for preparing a granulated compounding ingredient for vinyl chloxide resins by compounding a liquid or tacky additive into emulsion-polymerized polyvinyl chloride.
2. Description of the Prior Art -- 10 Using conventional techniques, it is necessary to add a lubricant to a vinyl chloride resin Eor us~ as a moldlng to improve the workability of the resin during working and also it is necessary to add a stabilizer such as an oryanotin stabili2er, etc., to a moulding vinyl chloride resin to prevent heat deterioration of the resin from occurring. However, slnce conventionally used additives such as a lubricant and an organotin stabilizer have a comparatively low melting point and such additives are mostly liquid or tacky at room ternpera-ture, (e.g., about 20-30C) such an additive is difficult to use.
More specifically, when a large amount of the additive is compounded in a vinyl chloride resin as it is, it is dlfficult to disperse the additive uniformly in the resin simply using agitation because a localized adhesion of the resin occurs.
This results in reducing the transportability of the product, hindering production, and decreasing the effects of stabilization of the resin.
In order to overcome the above described difficulty, a process ha~ been proposed in which a liquid additive such as an organotin stabilizer is mixed with a part of the resin using a mixer having a large shearing stress to form a master powder and ,,~, 1 then the master powder is blended with the remainder of the resin in a ribbon blender as described in, for example, Plastic Zairyo Koza (Plastic Mate_ al Course), 14, Vinyl Chlorid Resins;
pages 110-112, published hy Nikkan Koyyo Shinbun Sha on October 15 r 1961.
However, the above-described process has the following disadvantage. That is, in producing a master powder in a granulated condition which is non-tacky and which can be easily handled by compounding a liquid and tacky compounding ingredient in a portion of an ordinary moulding suspension-polymeri~ed vinyl chloride resin merely using the above-described process, only a master powder having a very low content of the com-pounding ingredient can be obtained and thus the advantage of forming the master powder cannot sufficiently be utilized. In c~mpounding a liquld ingredlent, the ratio of an amount of resin to that of a liquid ingredient is at most 85/15 by weight, in compounding a tacky ingredient, the ratio of an amount of resin to that of a tacky ingredient is at ~ost 70~30 by weight.
SUMMARY OF THE INVENTION
A primary object of this invention is, therefore, to provide a process for preparing a compounding ingredient for vinyl chloride resins containing therein a high conten-t of an additive or additives such as a stabilizer, etc., which is not tacky, and which is granulated for handling convenience.
That is, according to this invention, there is provided a process of preparing a compounding ingredient for vinyl chloride resins which comprises compounding a liquid or tacky additive or two or more additives comprising a par-tially or completely liquid or tacky additive or additives into an emulsion-
More specifically, when a large amount of the additive is compounded in a vinyl chloride resin as it is, it is dlfficult to disperse the additive uniformly in the resin simply using agitation because a localized adhesion of the resin occurs.
This results in reducing the transportability of the product, hindering production, and decreasing the effects of stabilization of the resin.
In order to overcome the above described difficulty, a process ha~ been proposed in which a liquid additive such as an organotin stabilizer is mixed with a part of the resin using a mixer having a large shearing stress to form a master powder and ,,~, 1 then the master powder is blended with the remainder of the resin in a ribbon blender as described in, for example, Plastic Zairyo Koza (Plastic Mate_ al Course), 14, Vinyl Chlorid Resins;
pages 110-112, published hy Nikkan Koyyo Shinbun Sha on October 15 r 1961.
However, the above-described process has the following disadvantage. That is, in producing a master powder in a granulated condition which is non-tacky and which can be easily handled by compounding a liquid and tacky compounding ingredient in a portion of an ordinary moulding suspension-polymeri~ed vinyl chloride resin merely using the above-described process, only a master powder having a very low content of the com-pounding ingredient can be obtained and thus the advantage of forming the master powder cannot sufficiently be utilized. In c~mpounding a liquld ingredlent, the ratio of an amount of resin to that of a liquid ingredient is at most 85/15 by weight, in compounding a tacky ingredient, the ratio of an amount of resin to that of a tacky ingredient is at ~ost 70~30 by weight.
SUMMARY OF THE INVENTION
A primary object of this invention is, therefore, to provide a process for preparing a compounding ingredient for vinyl chloride resins containing therein a high conten-t of an additive or additives such as a stabilizer, etc., which is not tacky, and which is granulated for handling convenience.
That is, according to this invention, there is provided a process of preparing a compounding ingredient for vinyl chloride resins which comprises compounding a liquid or tacky additive or two or more additives comprising a par-tially or completely liquid or tacky additive or additives into an emulsion-
3~ polymerized polyvinyl chloride powder under hesting.
`" ~ 6~
1 To this end, in one of its aspects, the invention provides a process for preparing a granulated and non-tacky : compounding ingredient for vinyl chloride resins which com~
prises compounding a liquid or tacky additive or two or more additives comprising a partially or completely liquid or tacky additive or additi~es with an emulsion-polymerized polyvinyl chloride powder under heating at a temperature of about 100 to 110C, wherein the compounding ratio of the polyvinyl chloride powder is 0.5 to 2 times the weight of the l.iquid or tacky additive or additives, wherein said additive or additives ~ comprise an organotin stabilizer or a mixture of an organotin - stabilizer with another additive or additives.
.: .
~' ' .
-2a-~i The emulsion-polymerized polyvinyl chloride powder which is used in this invention is a so-called resin for paste and the particles of the resin powder are compact spheres having a smooth surface. Particle size for the resin powder ranges 0.2 to 60 ~. The compounding ratio of the resin powder is generally 0.5 to 5 times by weight to the weight of the liquid or tacky additive or additives, preferably 1 to 2 times by weight.
The average degree of polymerization (Pn) of the polyvinyl chloride ~hich is useful in this invention ranges from 900 to 1700, preferably from 1200 to 1400. The molecular weight (Mw) calculated based on the average degree of polymerization ranges from 56250 to 106250, preferably from 75000 to 87500.
The copolymers used in this invention are those usually used as resins -Eor paste, for example, copolymers which are disclosed in Japanese Patent Publication 2338/74 (column 7, lines 7 to 19), i.e., a copolymer of vinyl chloride and a monomex other than vinyl chloride which is copolymerizable with vinyl chloride, such as an olefin, e.g., ethylene, propylene, n-butene and the like; a vinyl ester, e.g., vinyl acetake, vinyl propionate, vinyl laurate, vinyl stearate and the like;
an unsaturated acid and an ester thereof, e.g., acrylic acid, methacrylic acid, itaconic acid and the like; a vinyl ether, e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, lauryl vinyl ether and the like; maleic acid and anhydride thereof; fumaric acid and anhydride thereof; an aromatic vinyl;
an unsaturated carbonitrile or a mixture thereof.
The amount of monomer capable of copolymeri~lng with vinyl chloride is preferably below 50~ by weight based on the weight of the whole monomer.
A straight polymer of vinyl chloride is generally most preferred.
Examples of liquid or tacky additives to which this invention is applicable incl~de almost all organotin stabili~ers, for example, as a liquid additive octyltin mercaptide, octyltin maleate, dibutyltin malea~e, dioctyltin maleate, dibutyltin laurate, dibutyltin maleate laurate, dioctyltin laurate, dimethyltin carboxylic acid aster, dibu~yltin mercapto carboxylia acid ester, dibutyltin sulfide, dioctyltin mercaptida, dioctyltin sulfide and the like, and as a tacky additive, dibutyltin maleate polymer, dicotyltin ma~eate polymer and the like; other stabil-izers such as certain kinds of metal soaps, for example, as the liquid additive, calcium chlorostearate, barium chlorostearate and the like, and, as the tack~ additive, cadmium soap-epoxide and the like; and hydrocarbo~ type lubricants, for example, as the liquid additive, liquid paraffin and the lik~, and, as the tacky additive, polyethylene wax (low molecular weight poly-ethylene).
Examples of suitable mixers which can be used in compounding the additive and the polyvinyl chloride resin powder under heati.ng in this invention include a Henschel mixer, a super mixer, etc., with which mixing at high speed under heating can be achieved. It is preferred to compound the materials at about 100 to abou~ 110C. If the compounding is carried out at temperatures below about 100C., a tacky powder is obtained and if the compounding is carried out at temperature above about 110C., a block product which is not applicable for practical use unless it is applied to a grinding process is obtained.
Since the compounding ingredient prepared by the process of this invention has a high content of the additive or --4--.
29~
t additives such as a stabili~er, a lubricant, etc., is not tacky, and is comple~ely grallula~ed to obtain particles having a particle size distribution of 75 to 300 ,u, even in compounding the compounding ingreaient which is prepared using emulsion-polymerized pol~vinyl chloride according to this invention in a large amount of suspension-polymerized polyvinyl chloride usually employed in the ar~, the ingredient can be uniformly dispersed in the resin and hence no difficulties with respect to transportabili~y as well as production occur.
The invention is explained in greater detail by reference to the following examples.
In addition, emulsion-polymerized polyvinyl chloride having a mean polymerization degree of 1,300, a mean particle size of 50-60 microns, and an apparent specific gravity of 0.18 g/.ml. and suspension-polymerized polyvinyl chloride having a mean polymerixation degree of 800, a mean particle size of - 170 microns, and an apparent specific gravity of 0.54 g./ml.
were used in the examples.
2Q To 55 parts by weight of an emulsion-polymerized polyvinyl chloride powder was compounded 45 parts by weight of liguid octyltin mercaptide us~ng a Henschel mixer under heating employing the conditions as shown in Table lo The results obtained are also shown in Table 1 below.
In addition, for the sake of comparison, to 55 parts by weight of a suspension-polymerized polyvin~l chloride powder was compounded 45 parts by weight of liquid octyltin mercaptide under heating employing the same conditions as above and the results obtained are also shown in Table 1 below.
~' a) -,, ~ ~ ~D I E~ ~ l ~ __ . __ ... ... _... 1. ,... ~ .
~ . I ~ ~ . o o # Ln L o Ln ~ ~ ~ o o l 3 o ~ x _ ... . . ... ......... - ~, -1-- ----- o-~ o I E~ ~ ~,o ~ ~ ~ ' u o ~ C~ E
I ~1 Ln I ~ ~ E3 _ ~ . ____ _ .~ L____ __ ~ ~t----~ ~ , ~ IL.. ~ ~ I~ ?~ ~ ~o ~ ~ . ~V~' I r-i ~ ~ o a~
r l _ _ _ _~ -- ~ -t-- - -~ - ---- ---- ~ - --- - --- ---- -- - - ~ ----a) # o I ~ Ln n I r~l ?~ co ~ x r l x ¦ I ¦ r-l ~1 ~ ¦ ¦ c~ I ~ o ~ rl rl O
,~ ~ _ _1~ _ ~-- ! _ . . . __ ~ ~ ~:
P3 ~ Lr) . l f) o ~ ~ n~ o a) C) u~
E~ * ~n ~ r-l r l ts~ Lf~ ¦ ~ ~J ,~ ,~ 3 1 rl 20 r~ D ~ D ! ,~ E
l ~ O ~1 r~ 0 4 ~ O ~ C ¦~ ¦ ~ Q ~ C~
l r ~ ~ U t ~ ~ C
I ~ ~ L_~ tn c~ ~
I j ¦ O O ¦~ r,;) 4 ¦ *
L '~V !
, . _. _ - . - - - ---! .
2~6~
1 As iS clear from the results shown in Table l abo~e, .~ in Example l, a desirable granulated product which was not tacky was ohtained in each case, while i~ the comparison example, only a tacky block product was obtained in each case.
To 55 parts by weight of an emulsion-polymerized poIy-vinyl chloride powder were compounded 15 parts by weiyht o~
liquid octyltin mercaptide, 15 parts by weight of octyltin maleate as a tacky powder, and 15 parts by waight of a liquid hydrocargon lubricant (polyethylene wax of a molecular weight of 3000) using a Henschel mixer under heating employing the compounding conditions as shown in Table 2 below. The results obtained are shown in Table 2 below.
In addition, for the sake of comparison~ to 55 parts by weight of a suspension-polymerized polyvinyl chloride powder were compounded the sa~e additives as in the above example~
under heating employing the same compounding conditions as above and the results obtained are also shown in Table 2 below as Comparison Example 2. Moreover, to 85 parts by weight of 2~ a suspension-polymerized polyvinyl chloride powder were compounded 5 parts by weight of liquid octyltîn mercaptide, 5 parts by weight of octyltin maleate as a tacky powder, and 5 parts by weight of a liquid hydrocarbon lubricant under heating under the same compounding conditions as above and the results obtained are also shown in Table 2 below as Comparison Example 3.
Z~
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~ l Ln I Ln Ln Ln Ln ~ ~ ~1 Ln ~ I
~1~ * ~ ~ ~ ~D ~ lo !
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~ i Ln Ln Il') ~ Ll~ O U~) r-l r- r~l z _ co . ! ~, ,, ", N ~n O
l¢ ~ ____.. _____ _. ~ . _ .. ~ _.. ¦ .. . .__ . .. -o-- - .. . _ .. _ .. . I r :~ ~1 I L~ , Ln Ln ' Ln LO O ~1 ~1 Co r~
. g ~ , ~o j I ,i ~ ~n I ~l ~ o ~ ~ . I I I ~ I ~ i~
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1_ .... l___-_ __~- -- __ l--__-_l---------l -_.-_-_.i ~.. _ ` ._ ,., . _-~
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1 As is clear from the results shown in Table 2 above, when 45 parts by weight oE the liquid and tacky additives were compounded with 55 parts by weight of the emulsion-polymerized polyvinyl chloride powder under the compoundiny temperature conditions of 100 110C as in Example 1, a desirable granulated product which was not tacky was obtained in each case. On the other hand, when the same additives as in Example 2 were compounded with 55 parts by weight of suspension-polymerixed polyvinyl chloride under -~he same conditions as above as in Comparison Example 2, only a tacky block product was obtained in each case. When a comparatively small amount, i.e., 15 parts by weight of the same liquid and tacky additives were compounded with 85 parts by weight of suspension-polymerized polyvinyl chloride under the same conditions as above in Comparison Example 3, a granular non-tacky product was obtained in each case but the granular condition of the products was poor and the products were all inconvenient to handle.
As described above, by compounding liquid and tacky additives with the emulsion polymerized polyvinyl chloride powder under heating at 100-110C according to this invention desirable granulated compounding ingredients having a high additive content and which are not tacky can be obtained.
EXAMPLES 3 and 4 To 35 parts hy wei.ght of an emulsion-polymerized polyvinyl chloride powder were compounded 10 parts by weight of liquid octyltin mercaptide/ 10 parts by weight oE octyltin maleate as a tacky powder, 10 parts by weight of a liquid - hydrocarbon lubricant (polyethylene wax of a molecular weight of 3000), and 35 parts by weight of calcium carbonate powder using a Henschel mixer under heating employing the compounding .. . .
conditions as shown in Table 3 below. Furthermore, to 30 parts by weigh-t of an emulsion-polymeri~ed polyvinyl chloride powder were compounded 15 parts by weight of liquid octyltin mercaptide, 15 parts by weight of octyltin maleate as a tacky powder, 15 parts by weight of a liquid hydrocarbon lubricant ~polyethylene wax of a molecular weight of 3000), and ~5 parts by we.ight o:E
a silicic acid powder under the same conditions as above. The resul.ts obtained were shown in Table 3 below.
o 1 ' 6~L
o ~ n ~ . ~ ~ --~ - - , - -- -- - -- - ---- - 1-- - --i ~ O L~ j L L I ~ L~ O Ln Lf ) ~ ~O t~ I ~O
'X l l I . I ~1 ~D ~D lo .__ -~ - ~ ~ ~ -- ----- - --- 1'---'' ~
l o Ln n Ln I I L~ O ! O C0 iu~ ~ ~ ~ ~
* ~ lii i-i ~ l~i ln lo o ~ ~i ~o 1 Q ___L_ !. 1 ~i ~ ~ r _.
. .
I ! _ t t ~l ~ ~
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~:(r~ ~ IY7 I i. i , i i I ,_1 0 ~5 ~1 . CO
~ +~ . ---~ --- .-.----- ---~ - -----~ ~ ; ! I I I , j ! I~ i iO i.~i L') , O i O ! o ~ Ln l l o ' Ln ¦ ~ I L'~ t'r) i~ ~ i ~
i~ j ~ ~ i ~ ~ f ~ I i~ I jn I o I o ¦ ~ ¦ . ~ j r;
i~ll __L_I I_ -~------~-.--~---~--1-----~- ~-I _ j ~ I I l l I I f I i I L'~ , O ' O . O Ln l ~ O i O ~ O ¦ L~) ¦ ~ r I o ~ I ,~ ~ ,Ji l Ln I o ~ ¦ ~ r ~
I ~ f~i ! ~, ,1 ¦ Ln ~
I 1 i ;~ ~i v I .,~ I I tu I I i~ ~
o ~ f~ ~ ~ i ¦ 3 ~ f ~ ~ r, f i o S-i I a) S-i i i i ~ o s l ~ i i f ~1 1 o , ~, d Q ~ ~_ I Q, a ¦i Gi~ ~ ~ -- 5 ¦ u I o i ~i 1~ i ~ ¦~ i i, ri-r~ i f ~-rl ~ -ri ri ~ri l-rl ~ J f ~ I ~ i j ir.i ~ Il) f ~ a) ¦ ~1 a) j i~ tL) ~i 1~ ¦ V I ~ ! o i o i ~i i~ i a) ~ ~ _ I ~ ~ i U ~ L ~ ~;iJ i~ h ¦ L~ ~
I ~ .___ _.. _ ~___._._._.. _.. _ _.~.. ~_._.___.. _ _.1__ __.___.. .. _ _.__.____ I I if i~ ~, ¦ ri ~ fi Il 1 5i s ~ LJ~ I .
3 t3 1 1 1 0 0 1 o i -i v L ~ ~u~ ~
___ ___ _.
1 As is c.lear from the results shown in Table 3 above, when a powdery filler such as calcium carbonate powder and silicic acid powder was compounded with the emulsion-polymerized polyvinyl chloride powder together wi~h other liquid and tacky additives according to the process of this invention, desirable granulated compounding inyredients having a high additive content such as the above described liquid and tacky stabilizers, lubricant, etc., and which are not tacky can be obtained.
While the invention has been described in detail and 1~ with reference to specific emboidments thereof~ it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
`" ~ 6~
1 To this end, in one of its aspects, the invention provides a process for preparing a granulated and non-tacky : compounding ingredient for vinyl chloride resins which com~
prises compounding a liquid or tacky additive or two or more additives comprising a partially or completely liquid or tacky additive or additi~es with an emulsion-polymerized polyvinyl chloride powder under heating at a temperature of about 100 to 110C, wherein the compounding ratio of the polyvinyl chloride powder is 0.5 to 2 times the weight of the l.iquid or tacky additive or additives, wherein said additive or additives ~ comprise an organotin stabilizer or a mixture of an organotin - stabilizer with another additive or additives.
.: .
~' ' .
-2a-~i The emulsion-polymerized polyvinyl chloride powder which is used in this invention is a so-called resin for paste and the particles of the resin powder are compact spheres having a smooth surface. Particle size for the resin powder ranges 0.2 to 60 ~. The compounding ratio of the resin powder is generally 0.5 to 5 times by weight to the weight of the liquid or tacky additive or additives, preferably 1 to 2 times by weight.
The average degree of polymerization (Pn) of the polyvinyl chloride ~hich is useful in this invention ranges from 900 to 1700, preferably from 1200 to 1400. The molecular weight (Mw) calculated based on the average degree of polymerization ranges from 56250 to 106250, preferably from 75000 to 87500.
The copolymers used in this invention are those usually used as resins -Eor paste, for example, copolymers which are disclosed in Japanese Patent Publication 2338/74 (column 7, lines 7 to 19), i.e., a copolymer of vinyl chloride and a monomex other than vinyl chloride which is copolymerizable with vinyl chloride, such as an olefin, e.g., ethylene, propylene, n-butene and the like; a vinyl ester, e.g., vinyl acetake, vinyl propionate, vinyl laurate, vinyl stearate and the like;
an unsaturated acid and an ester thereof, e.g., acrylic acid, methacrylic acid, itaconic acid and the like; a vinyl ether, e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, lauryl vinyl ether and the like; maleic acid and anhydride thereof; fumaric acid and anhydride thereof; an aromatic vinyl;
an unsaturated carbonitrile or a mixture thereof.
The amount of monomer capable of copolymeri~lng with vinyl chloride is preferably below 50~ by weight based on the weight of the whole monomer.
A straight polymer of vinyl chloride is generally most preferred.
Examples of liquid or tacky additives to which this invention is applicable incl~de almost all organotin stabili~ers, for example, as a liquid additive octyltin mercaptide, octyltin maleate, dibutyltin malea~e, dioctyltin maleate, dibutyltin laurate, dibutyltin maleate laurate, dioctyltin laurate, dimethyltin carboxylic acid aster, dibu~yltin mercapto carboxylia acid ester, dibutyltin sulfide, dioctyltin mercaptida, dioctyltin sulfide and the like, and as a tacky additive, dibutyltin maleate polymer, dicotyltin ma~eate polymer and the like; other stabil-izers such as certain kinds of metal soaps, for example, as the liquid additive, calcium chlorostearate, barium chlorostearate and the like, and, as the tack~ additive, cadmium soap-epoxide and the like; and hydrocarbo~ type lubricants, for example, as the liquid additive, liquid paraffin and the lik~, and, as the tacky additive, polyethylene wax (low molecular weight poly-ethylene).
Examples of suitable mixers which can be used in compounding the additive and the polyvinyl chloride resin powder under heati.ng in this invention include a Henschel mixer, a super mixer, etc., with which mixing at high speed under heating can be achieved. It is preferred to compound the materials at about 100 to abou~ 110C. If the compounding is carried out at temperatures below about 100C., a tacky powder is obtained and if the compounding is carried out at temperature above about 110C., a block product which is not applicable for practical use unless it is applied to a grinding process is obtained.
Since the compounding ingredient prepared by the process of this invention has a high content of the additive or --4--.
29~
t additives such as a stabili~er, a lubricant, etc., is not tacky, and is comple~ely grallula~ed to obtain particles having a particle size distribution of 75 to 300 ,u, even in compounding the compounding ingreaient which is prepared using emulsion-polymerized pol~vinyl chloride according to this invention in a large amount of suspension-polymerized polyvinyl chloride usually employed in the ar~, the ingredient can be uniformly dispersed in the resin and hence no difficulties with respect to transportabili~y as well as production occur.
The invention is explained in greater detail by reference to the following examples.
In addition, emulsion-polymerized polyvinyl chloride having a mean polymerization degree of 1,300, a mean particle size of 50-60 microns, and an apparent specific gravity of 0.18 g/.ml. and suspension-polymerized polyvinyl chloride having a mean polymerixation degree of 800, a mean particle size of - 170 microns, and an apparent specific gravity of 0.54 g./ml.
were used in the examples.
2Q To 55 parts by weight of an emulsion-polymerized polyvinyl chloride powder was compounded 45 parts by weight of liguid octyltin mercaptide us~ng a Henschel mixer under heating employing the conditions as shown in Table lo The results obtained are also shown in Table 1 below.
In addition, for the sake of comparison, to 55 parts by weight of a suspension-polymerized polyvin~l chloride powder was compounded 45 parts by weight of liquid octyltin mercaptide under heating employing the same conditions as above and the results obtained are also shown in Table 1 below.
~' a) -,, ~ ~ ~D I E~ ~ l ~ __ . __ ... ... _... 1. ,... ~ .
~ . I ~ ~ . o o # Ln L o Ln ~ ~ ~ o o l 3 o ~ x _ ... . . ... ......... - ~, -1-- ----- o-~ o I E~ ~ ~,o ~ ~ ~ ' u o ~ C~ E
I ~1 Ln I ~ ~ E3 _ ~ . ____ _ .~ L____ __ ~ ~t----~ ~ , ~ IL.. ~ ~ I~ ?~ ~ ~o ~ ~ . ~V~' I r-i ~ ~ o a~
r l _ _ _ _~ -- ~ -t-- - -~ - ---- ---- ~ - --- - --- ---- -- - - ~ ----a) # o I ~ Ln n I r~l ?~ co ~ x r l x ¦ I ¦ r-l ~1 ~ ¦ ¦ c~ I ~ o ~ rl rl O
,~ ~ _ _1~ _ ~-- ! _ . . . __ ~ ~ ~:
P3 ~ Lr) . l f) o ~ ~ n~ o a) C) u~
E~ * ~n ~ r-l r l ts~ Lf~ ¦ ~ ~J ,~ ,~ 3 1 rl 20 r~ D ~ D ! ,~ E
l ~ O ~1 r~ 0 4 ~ O ~ C ¦~ ¦ ~ Q ~ C~
l r ~ ~ U t ~ ~ C
I ~ ~ L_~ tn c~ ~
I j ¦ O O ¦~ r,;) 4 ¦ *
L '~V !
, . _. _ - . - - - ---! .
2~6~
1 As iS clear from the results shown in Table l abo~e, .~ in Example l, a desirable granulated product which was not tacky was ohtained in each case, while i~ the comparison example, only a tacky block product was obtained in each case.
To 55 parts by weight of an emulsion-polymerized poIy-vinyl chloride powder were compounded 15 parts by weiyht o~
liquid octyltin mercaptide, 15 parts by weight of octyltin maleate as a tacky powder, and 15 parts by waight of a liquid hydrocargon lubricant (polyethylene wax of a molecular weight of 3000) using a Henschel mixer under heating employing the compounding conditions as shown in Table 2 below. The results obtained are shown in Table 2 below.
In addition, for the sake of comparison~ to 55 parts by weight of a suspension-polymerized polyvinyl chloride powder were compounded the sa~e additives as in the above example~
under heating employing the same compounding conditions as above and the results obtained are also shown in Table 2 below as Comparison Example 2. Moreover, to 85 parts by weight of 2~ a suspension-polymerized polyvinyl chloride powder were compounded 5 parts by weight of liquid octyltîn mercaptide, 5 parts by weight of octyltin maleate as a tacky powder, and 5 parts by weight of a liquid hydrocarbon lubricant under heating under the same compounding conditions as above and the results obtained are also shown in Table 2 below as Comparison Example 3.
Z~
_ I I ~ 1~ 1 r~ _ l o o o Ln ~1 r~) ~D I
~ l Ln I Ln Ln Ln Ln ~ ~ ~1 Ln ~ I
~1~ * ~ ~ ~ ~D ~ lo !
~; ~ -r~ ------------ ---------- ----------- --- -- ---- ------- -------- -------- ------- ---------- ------- -------- J
. X l l . ~ I~ r O ~0 d~ Ln ) ~ ~ ~D
~ i Ln Ln Il') ~ Ll~ O U~) r-l r- r~l z _ co . ! ~, ,, ", N ~n O
l¢ ~ ____.. _____ _. ~ . _ .. ~ _.. ¦ .. . .__ . .. -o-- - .. . _ .. _ .. . I r :~ ~1 I L~ , Ln Ln ' Ln LO O ~1 ~1 Co r~
. g ~ , ~o j I ,i ~ ~n I ~l ~ o ~ ~ . I I I ~ I ~ i~
LO ¦ Ln L~ ' Ln ~ o j o o Ln I ~ O
~_ Ln I ~1 ~ 1 , Ln I ~1 ~r ~
. ~ ~ __ _~ _ L . .~ . .. --.--!---.. -.. -.. ~ ~ 1 ~D I ~ ~ L
I I I- - T -- -1-------- ~
~ i I ~ ~ .
¦ ~n ¦ ~l ~ o ¦ Ln ~ t H ¦ ~ J
~ I ,~
I ~il-J I I LO I LO ~ I O I ~ O ~ I ~ i I
0l~ O I 1 '` ¦ Ir~ I Ln ~ I ¦ L') ! Ln ~ Ln ! o I o 1~ I Ln~ ~ ¦ r ~ .
Ln i ~ Lr~ ri ~ ~ I 1~ ;
1_ .... l___-_ __~- -- __ l--__-_l---------l -_.-_-_.i ~.. _ ` ._ ,., . _-~
1 ~ I Ln i ~ I "~ Ln i n I o ! Ln l o I Lnl ~ I~D 1 ,~ 1 Ln ~ Lf'l j O ~ r-ll ~ o ~ I ~ ho ~ I ~ Pi ~ I~ ~ o~
0 --I ~ I C2~ -rJ U ~ N
L ~ ~0 31 o 3 Lo 3 I >1 3 30 ~ ~ O ~
I. I o o o o~ I
O V ~ ~
~ J
1 As is clear from the results shown in Table 2 above, when 45 parts by weight oE the liquid and tacky additives were compounded with 55 parts by weight of the emulsion-polymerized polyvinyl chloride powder under the compoundiny temperature conditions of 100 110C as in Example 1, a desirable granulated product which was not tacky was obtained in each case. On the other hand, when the same additives as in Example 2 were compounded with 55 parts by weight of suspension-polymerixed polyvinyl chloride under -~he same conditions as above as in Comparison Example 2, only a tacky block product was obtained in each case. When a comparatively small amount, i.e., 15 parts by weight of the same liquid and tacky additives were compounded with 85 parts by weight of suspension-polymerized polyvinyl chloride under the same conditions as above in Comparison Example 3, a granular non-tacky product was obtained in each case but the granular condition of the products was poor and the products were all inconvenient to handle.
As described above, by compounding liquid and tacky additives with the emulsion polymerized polyvinyl chloride powder under heating at 100-110C according to this invention desirable granulated compounding ingredients having a high additive content and which are not tacky can be obtained.
EXAMPLES 3 and 4 To 35 parts hy wei.ght of an emulsion-polymerized polyvinyl chloride powder were compounded 10 parts by weight of liquid octyltin mercaptide/ 10 parts by weight oE octyltin maleate as a tacky powder, 10 parts by weight of a liquid - hydrocarbon lubricant (polyethylene wax of a molecular weight of 3000), and 35 parts by weight of calcium carbonate powder using a Henschel mixer under heating employing the compounding .. . .
conditions as shown in Table 3 below. Furthermore, to 30 parts by weigh-t of an emulsion-polymeri~ed polyvinyl chloride powder were compounded 15 parts by weight of liquid octyltin mercaptide, 15 parts by weight of octyltin maleate as a tacky powder, 15 parts by weight of a liquid hydrocarbon lubricant ~polyethylene wax of a molecular weight of 3000), and ~5 parts by we.ight o:E
a silicic acid powder under the same conditions as above. The resul.ts obtained were shown in Table 3 below.
o 1 ' 6~L
o ~ n ~ . ~ ~ --~ - - , - -- -- - -- - ---- - 1-- - --i ~ O L~ j L L I ~ L~ O Ln Lf ) ~ ~O t~ I ~O
'X l l I . I ~1 ~D ~D lo .__ -~ - ~ ~ ~ -- ----- - --- 1'---'' ~
l o Ln n Ln I I L~ O ! O C0 iu~ ~ ~ ~ ~
* ~ lii i-i ~ l~i ln lo o ~ ~i ~o 1 Q ___L_ !. 1 ~i ~ ~ r _.
. .
I ! _ t t ~l ~ ~
~ in ¦ o i o ~ o Ln ¦ ~ o I o I i~ i~n ~ ~
~:(r~ ~ IY7 I i. i , i i I ,_1 0 ~5 ~1 . CO
~ +~ . ---~ --- .-.----- ---~ - -----~ ~ ; ! I I I , j ! I~ i iO i.~i L') , O i O ! o ~ Ln l l o ' Ln ¦ ~ I L'~ t'r) i~ ~ i ~
i~ j ~ ~ i ~ ~ f ~ I i~ I jn I o I o ¦ ~ ¦ . ~ j r;
i~ll __L_I I_ -~------~-.--~---~--1-----~- ~-I _ j ~ I I l l I I f I i I L'~ , O ' O . O Ln l ~ O i O ~ O ¦ L~) ¦ ~ r I o ~ I ,~ ~ ,Ji l Ln I o ~ ¦ ~ r ~
I ~ f~i ! ~, ,1 ¦ Ln ~
I 1 i ;~ ~i v I .,~ I I tu I I i~ ~
o ~ f~ ~ ~ i ¦ 3 ~ f ~ ~ r, f i o S-i I a) S-i i i i ~ o s l ~ i i f ~1 1 o , ~, d Q ~ ~_ I Q, a ¦i Gi~ ~ ~ -- 5 ¦ u I o i ~i 1~ i ~ ¦~ i i, ri-r~ i f ~-rl ~ -ri ri ~ri l-rl ~ J f ~ I ~ i j ir.i ~ Il) f ~ a) ¦ ~1 a) j i~ tL) ~i 1~ ¦ V I ~ ! o i o i ~i i~ i a) ~ ~ _ I ~ ~ i U ~ L ~ ~;iJ i~ h ¦ L~ ~
I ~ .___ _.. _ ~___._._._.. _.. _ _.~.. ~_._.___.. _ _.1__ __.___.. .. _ _.__.____ I I if i~ ~, ¦ ri ~ fi Il 1 5i s ~ LJ~ I .
3 t3 1 1 1 0 0 1 o i -i v L ~ ~u~ ~
___ ___ _.
1 As is c.lear from the results shown in Table 3 above, when a powdery filler such as calcium carbonate powder and silicic acid powder was compounded with the emulsion-polymerized polyvinyl chloride powder together wi~h other liquid and tacky additives according to the process of this invention, desirable granulated compounding inyredients having a high additive content such as the above described liquid and tacky stabilizers, lubricant, etc., and which are not tacky can be obtained.
While the invention has been described in detail and 1~ with reference to specific emboidments thereof~ it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (7)
1. A process for preparing a granulated and non-tacky compounding ingredient for vinyl chloride resins which comprises compounding a liquid or tacky additive or two or more additives comprising a partially or completely liquid or tacky additive or additives with an emulsion-polymerized polyvinyl chloride powder under heating at a temperature of about 100 to 110°C, wherein the compounding ratio of the polyvinyl chloride powder is 0.5 to 2 times the weight of the liquid or tacky additive or additives, wherein said additive or additives are selected from the group consisting of an organotin stabilizer selected from the group consisting of octyltin mercaptide, octyltin maleate, dibutyltin maleate, dioctyltin maleate, dibutyltin laurate, dibutyltin maleate laurate, dioctyltin laurate, dimethyltin carboxylic acid ester, dibutyltin mercapto carboxylic acid ester, dibutyltin sulfide, dioctyltin mercaptide, dioctyltin sulfide, dibutyltin maleate polymer,dicotyltin maleate polymer; and a mixture of an organotin stabilizer as hereinbefore defined and at least one other additive, said at least one other additive selected from the group consisting of metal soaps selected from the group con-sisting of calcium chlorostearate, barium chlorostearate,cadmium soap-epoxide; and hydrocarbon type lubricants selected from the group consisting of liquid paraffin and polyethylene wax.
2. A process as claimed in claim 1 wherein said organotin stabilizer is octyltin mercaptide or octyltin maleate.
3. A process for preparing a compounding ingredient for vinyl chloride resins as claimed in claim 1, wherein the polyvinyl chloride powder has a particle size of 0.2 to 60µ.
4. A process for preparing a compounding ingredient for vinyl chloride resins as claimed in claim 3, wherein the granu-lated compounding ingredient has a particle size distribution of 75 to 300µ.
5. A process as claimed in claim 1, wherein the average degree of polymerization of said polyvinyl chloride is from 900 to 1700.
6. A process as claimed in claim 1, wherein said at least one other additive includes the hydrocarbon type lubricant.
7. In a process of compounding a compounding ingredient into a suspension-polymerized polyvinyl chloride, the improvement wherein said compounding ingredient is produced by the process comprising preparing a granulated and non-tacky compounding ingredient for vinyl chloride resins which comprises compounding a liquid or tacky additive or two or more additives comprising a partially or completely liquid or tacky additive or additives with an emulsion polymerized polyvinyl chloride powder under heating at a temperature of about 100 to about 110°C, wherein the compounding ratio of the polyvinyl chloride powder is 0.5 to 2 times the weight of the liquid or tacky additive or additives, wherein said additive or additives are selected from the group consisting of an organotin stabilizer selected from the group consisting of octyltin mercaptide, octyltin maleate, dibutyltin maleate, dioctyltin maleate, dibutyltin laurate, dibutyltin maleate laurate, dioctyltin laurate, dimethyltin carboxylic acid ester, dibutyltin mercapto caboxylic acid ester, dibutyltin sulfide, dioctyltin mercaptide, dioctyltin sulfide, dibutyltin maleate polymer,dicotyltin maleate polymer; and a mixture of an organotin stabilizer as hereinbefore defined and at least one other additive, said at least one other additive selected from
7. In a process of compounding a compounding ingredient into a suspension-polymerized polyvinyl chloride, the improvement wherein said compounding ingredient is produced by the process comprising preparing a granulated and non-tacky compounding ingredient for vinyl chloride resins which comprises compounding a liquid or tacky additive or two or more additives comprising a partially or completely liquid or tacky additive or additives with an emulsion polymerized polyvinyl chloride powder under heating at a temperature of about 100 to about 110°C, wherein the compounding ratio of the polyvinyl chloride powder is 0.5 to 2 times the weight of the liquid or tacky additive or additives, wherein said additive or additives are selected from the group consisting of an organotin stabilizer selected from the group consisting of octyltin mercaptide, octyltin maleate, dibutyltin maleate, dioctyltin maleate, dibutyltin laurate, dibutyltin maleate laurate, dioctyltin laurate, dimethyltin carboxylic acid ester, dibutyltin mercapto caboxylic acid ester, dibutyltin sulfide, dioctyltin mercaptide, dioctyltin sulfide, dibutyltin maleate polymer,dicotyltin maleate polymer; and a mixture of an organotin stabilizer as hereinbefore defined and at least one other additive, said at least one other additive selected from
Claim 7 continued....
the group consisting of metal soaps selected from the group con-sisting of calcium chlorostearate, barium chlorostearate,cadmium soap-epoxide; and hydrocarbon type lubricants selected from the group consisting of liquid paraffin and polyethylene wax.
the group consisting of metal soaps selected from the group con-sisting of calcium chlorostearate, barium chlorostearate,cadmium soap-epoxide; and hydrocarbon type lubricants selected from the group consisting of liquid paraffin and polyethylene wax.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29681/76 | 1976-03-17 | ||
| JP2968176A JPS52111953A (en) | 1976-03-17 | 1976-03-17 | Preparation of compounding additives for vinyl chloride resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102461A true CA1102461A (en) | 1981-06-02 |
Family
ID=12282848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,912A Expired CA1102461A (en) | 1976-03-17 | 1977-03-14 | Process for preparing compounding ingredients for vinyl chloride resins |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS52111953A (en) |
| AU (1) | AU504155B2 (en) |
| CA (1) | CA1102461A (en) |
| DE (1) | DE2711775C3 (en) |
| ES (1) | ES456962A1 (en) |
| FR (1) | FR2344592A1 (en) |
| GB (1) | GB1573174A (en) |
| IT (1) | IT1083734B (en) |
| NL (1) | NL165199C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60500247A (en) * | 1982-02-01 | 1985-02-28 | ブス アクチエンゲゼルシヤフト | Method and apparatus for continuous production of flowable homogeneous mixture of plastic and additives |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE563999A (en) * | 1957-01-18 | |||
| US3301813A (en) * | 1963-03-22 | 1967-01-31 | Monsanto Co | Process for incorporating a liquid additive into a solid thermoplastic polymer |
| FR1429010A (en) * | 1964-03-30 | 1966-02-18 | Knapsack Ag | Process for the preparation of mixtures based on vinyl resins containing adjuvants |
| BE769094A (en) * | 1970-07-06 | 1971-11-03 | Reagens Spa | PROCESS FOR PACKAGING ADDITIVES AND ADDITIVES CONDITIONED BY THE PROCESS |
-
1976
- 1976-03-17 JP JP2968176A patent/JPS52111953A/en active Pending
-
1977
- 1977-03-14 CA CA273,912A patent/CA1102461A/en not_active Expired
- 1977-03-15 IT IT4847277A patent/IT1083734B/en active
- 1977-03-16 GB GB1106777A patent/GB1573174A/en not_active Expired
- 1977-03-16 AU AU23300/77A patent/AU504155B2/en not_active Expired
- 1977-03-17 DE DE19772711775 patent/DE2711775C3/en not_active Expired
- 1977-03-17 ES ES456962A patent/ES456962A1/en not_active Expired
- 1977-03-17 NL NL7702899A patent/NL165199C/en not_active IP Right Cessation
- 1977-03-17 FR FR7708043A patent/FR2344592A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL165199B (en) | 1980-10-15 |
| IT1083734B (en) | 1985-05-25 |
| DE2711775A1 (en) | 1977-09-22 |
| AU2330077A (en) | 1978-09-21 |
| GB1573174A (en) | 1980-08-20 |
| DE2711775B2 (en) | 1980-03-06 |
| JPS52111953A (en) | 1977-09-20 |
| NL7702899A (en) | 1977-09-20 |
| FR2344592A1 (en) | 1977-10-14 |
| AU504155B2 (en) | 1979-10-04 |
| FR2344592B1 (en) | 1981-09-11 |
| ES456962A1 (en) | 1978-01-16 |
| NL165199C (en) | 1981-03-16 |
| DE2711775C3 (en) | 1986-01-09 |
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