CA1051580A - Thermoplastic composition consisting of a vinyl chloride polymer and a chlorinated low pressure polyethylene - Google Patents
Thermoplastic composition consisting of a vinyl chloride polymer and a chlorinated low pressure polyethyleneInfo
- Publication number
- CA1051580A CA1051580A CA207,124A CA207124A CA1051580A CA 1051580 A CA1051580 A CA 1051580A CA 207124 A CA207124 A CA 207124A CA 1051580 A CA1051580 A CA 1051580A
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- Prior art keywords
- weight
- thermoplastic composition
- vinyl chloride
- polyethylene
- low pressure
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic composition Abstract of the disclosure Thermoplastic compositions essentially consisting of vinyl chloride copolymers and chlorinated low pressure poly-ethylene having a reduced specific viscosity of from 1 to 5 dl/g,a residue value of from 2 to 40% and a swelling value of from 10 to 70%,which chlorinated polyethylene is prepared in chlorhydric acid, optionally in the presence of silicic acid and siloxane oil.
The compositions according to the invention are well suit-able for the dry-blend technique. They may be used for making pipel, profiles, plates, sheets, cables, flexible tubes, injection moulded particles and other shapes and structures.
The compositions according to the invention are well suit-able for the dry-blend technique. They may be used for making pipel, profiles, plates, sheets, cables, flexible tubes, injection moulded particles and other shapes and structures.
Description
HOE 73iF 264 l~S~580 g Thi~ invention relatQq to a th~rmopla~tic compositlon con-sisting of a vinyl chloride polymer and ~ chlorinated low pres-sure polyethylene.
It has been proposed to elastify polyvinyl chloride and vinyl chloride copolymers by the addition of chlorination pro-ductY of polyolefins obtained by chlorinating polyolefins in aqueous suspension and having a chlorine content of from 25 to 50 % by weight (cf. German Patent 1,469,990 and German Patents 1,236,774 and 1,266,969).
To obtain chlorination products having a good elastifying .
effect combined with a sufficient fineness o~ grain ~he chlorin-ation has to be carried out in the presence of fine-grained inert, inorganic or organic additives to ~void agglomeration.
As inorganic additives silicic acid or kieselguhr have been proposed (cf. ~erman Patent 1,420,407).
The relatively 1arge amount of silicic acid, whcih must be added to the ch~ination reaction as anti-agglomeration agent and which partially remains in the final blend when the chloro-polyolefln i~ mixed with polyvinyl chloride, haq a detrimental ef~ect on the rheological and mechanical p~operties of the blend.
It has now been ~ound that mixtures o~ ~rinyl chloride poly-mers and chlorination products o~ polyole~ins can be produced which d~hot have the a~oresaid disadvanta~es and are well suitable for dry blend ~echnique by using ~ chlorinated low pressure polyethylene prepared by chlorina~ing in aqueous hyd*o- ~ :
chloric acid, pre~erably in the presence ~ silicic acid having a large sur~ace ~nd a si'oxane oil.
2g The present in~ention provides a thermoplastic composition - ~
. ,; , `: ~ ' ; .` , ' ' ' ; . ' ' '' ' ~ -`' ;:'; ' '; ' ., ~ :.
: ' `. . . ''' ,'; ' ` ` '` '' .:., ...... ., , ''~ ' '-. ,' .
'` ' .'. ' ' ' : ' . HOE 73/F 264 105~
essentially consisting of a) 98 to 50 % b~ weight of a vinyl chloride polymer and b) 2 to 50 ~ by weight of a chlorinated low pressure poly-ethylane. havlng a chlorine content of 25 to 42 % by weight, a reduced specific viscosity o~ 1 to 5 dl/g, a residue value of 2 to 40 %, measured by extraction with toluene~ i acetone in a proportion of 1 : 19 and a swelling value of ,;
10 to 70 ~, measured in methylcyclohexane, and obtained by chlorinating a low prcssure polyethylene in aqueous hydro-chloric acid having a strength of from 10 to 35 ~, preferably 15 to 30 ~ in the presence of O to 2 ~ by w0ight of silicic acid and O to 1.0 % by weight of a siloxane oil, the percentages ~.
being calculated on the low pressure pol~-e~ylene used, at a chlorination temperature of from 50 to 130C, at least 10 % by welght of chlorine being incorporated at a tamperature of from 120 to 130C.
,:
The present invention also provides a process for the manufacture of a thermoplastic composition by mi~ing .
a) 98 to 50 ~ by weight of a vinyl chloride polymer and b) 2 to 50 ~ by we~ght of a chlorinated low pressurs poly-, ethylene ha~ing a chlorine content of from 25 to 42 % by weight, a re-duced speci~ic viqco~ity of 1 to 5 dl~g, a residue value of from
It has been proposed to elastify polyvinyl chloride and vinyl chloride copolymers by the addition of chlorination pro-ductY of polyolefins obtained by chlorinating polyolefins in aqueous suspension and having a chlorine content of from 25 to 50 % by weight (cf. German Patent 1,469,990 and German Patents 1,236,774 and 1,266,969).
To obtain chlorination products having a good elastifying .
effect combined with a sufficient fineness o~ grain ~he chlorin-ation has to be carried out in the presence of fine-grained inert, inorganic or organic additives to ~void agglomeration.
As inorganic additives silicic acid or kieselguhr have been proposed (cf. ~erman Patent 1,420,407).
The relatively 1arge amount of silicic acid, whcih must be added to the ch~ination reaction as anti-agglomeration agent and which partially remains in the final blend when the chloro-polyolefln i~ mixed with polyvinyl chloride, haq a detrimental ef~ect on the rheological and mechanical p~operties of the blend.
It has now been ~ound that mixtures o~ ~rinyl chloride poly-mers and chlorination products o~ polyole~ins can be produced which d~hot have the a~oresaid disadvanta~es and are well suitable for dry blend ~echnique by using ~ chlorinated low pressure polyethylene prepared by chlorina~ing in aqueous hyd*o- ~ :
chloric acid, pre~erably in the presence ~ silicic acid having a large sur~ace ~nd a si'oxane oil.
2g The present in~ention provides a thermoplastic composition - ~
. ,; , `: ~ ' ; .` , ' ' ' ; . ' ' '' ' ~ -`' ;:'; ' '; ' ., ~ :.
: ' `. . . ''' ,'; ' ` ` '` '' .:., ...... ., , ''~ ' '-. ,' .
'` ' .'. ' ' ' : ' . HOE 73/F 264 105~
essentially consisting of a) 98 to 50 % b~ weight of a vinyl chloride polymer and b) 2 to 50 ~ by weight of a chlorinated low pressure poly-ethylane. havlng a chlorine content of 25 to 42 % by weight, a reduced specific viscosity o~ 1 to 5 dl/g, a residue value of 2 to 40 %, measured by extraction with toluene~ i acetone in a proportion of 1 : 19 and a swelling value of ,;
10 to 70 ~, measured in methylcyclohexane, and obtained by chlorinating a low prcssure polyethylene in aqueous hydro-chloric acid having a strength of from 10 to 35 ~, preferably 15 to 30 ~ in the presence of O to 2 ~ by w0ight of silicic acid and O to 1.0 % by weight of a siloxane oil, the percentages ~.
being calculated on the low pressure pol~-e~ylene used, at a chlorination temperature of from 50 to 130C, at least 10 % by welght of chlorine being incorporated at a tamperature of from 120 to 130C.
,:
The present invention also provides a process for the manufacture of a thermoplastic composition by mi~ing .
a) 98 to 50 ~ by weight of a vinyl chloride polymer and b) 2 to 50 ~ by we~ght of a chlorinated low pressurs poly-, ethylene ha~ing a chlorine content of from 25 to 42 % by weight, a re-duced speci~ic viqco~ity of 1 to 5 dl~g, a residue value of from
2 to 40 %, measured by extraction with toluene/acetone in a proportion of 1 : 1, and a swelling valu~ of ~rom 10 to 70 %, measured in methylcyclohexane, prepared by chlorinating a pre-~erably fine-grained low pressure polyeth~lene in aqueous hydro-chloric acid of`10 to 35 ~, preferabl~ 15 to 30 ~, ~trength in Z~ the presence of O to ~ % by weight of silioic acid and O to 1.0~ -~, _ 3 _ `- ' .:. :. ' . - . . .
~ ~ . -- - : . :
- ' : . : ~ :' ~OE 73/F 264 ~(~5~5~ilV ~ ' by weight of a i~iloxane oil, the p~rcentag0s being calculated on the starting polyethylene~ at a chlorinatlon temperature o~
from 50 *o 130C, the low presiqure polyethylene being possibly thermally treated or prssintered at a temperature in the range o~ from 100C~-i~ cryAtallite melting point and at least 10 %
of the chlorine being incorporated at a temperature of from 120 to 130C~
The thermoplastic composition consists of 98 to j50 % by weight pre~erably 95to 80 % by weigh*,of polyvinyl chloride or a copolymer o~ vinyl chloride with other comonomers, such as vinyl acetate acrylic acid esters or methacrylic acid esters, the amount o~ comonomer units in the polymer being at most 20 by weight, preferably 1 to 5 % by weight. The K value o~ the polymer is expediently in a ranga o~ from 50 to 80.
The remainlng ~ to 50 % by weight, pr~ferably 2 to 20 ~ by ~`
weight o~ the thermoplastic composition of the invention consists of a chlorinated low pressure polyethylene o~ high molecular weight containing 25 to 42 % by weight, p~ferably 30 to 40 $
by weight,o~ chlorine. The distribution o~ the chlorine atomes ~;
2n in the polyethylene grains, i.e. the degr~e of "pen~rating or through chlorination" iq oharacterizèd by the reisidue value according to the toluene/acetone method and the swelling value ~ ;
in methylcyclohexan~. The chlorinated low ~resqure polyethylene suitable for making the compositions of the invention shall have a residue value of 2 to 40 ~, pre~erably 2 to 30 %, and a swel-llng value of 10 to 70 %, pre~erably 20 to 50 %. ~oreover, it shall have a reduced specific viscosity o~ 1 to 5 dl/g, pre-~erably 1 to ~.5 dljg.
29 The chlorinated low pre~ure polyethylene o~ high molecular .
:: . :` . `~ .:. `. ` --~: ` - ` ` ' ` . ` , ,, .:
~:" ` ` :'. `, . . `, , , ~
-" ~0515~0.
~eight is fins-grainQd and-can readily b~ mi~ed homogeneously with the ~inyl chloride polymer powder.
The chlorinated low pressure polyethylene to be used according to the invention is produced ~y chlorinatin~ ~ne-grained low pressure polyethylene, ~hich may have been therm-ally treated or pre-sintered for 5 to 300 minutes at a temper-ature of from 100 C to its crystallite melting point (cf.German Offenlegungsschrift 1,720,800), in hydrochloric acid expedi-`ently 3 to 30 times the amount of acid is used, referred to the low pressure polyethylene. The chlorination is started at a temperature of from 50 to 100C and terminated at 120 to 130C.
The chlorination is advantageously started in a temper-ature range of from 70 to 90C, continued with continual temperature increase and terminated at ~ t~mperature ranging from 120 to l30 C, Alternati~ely, the chlorination can be effected in two steps, i.e, it is started at a temperature of from 50C to 100 C, the chlorine supply is interrupted while the temperature is raised to 120 to 130C and the chlorination i9 then conti~ued and terminated at that temperature.
The low pressure polyethylene used as starting material ha~ a reduced specific viscosity of 1 to ~ dl/g, preferably 1 to 3.5 dl/g-By silicic acid present in the chlo~ination as agglomer-ation inhibitor the ~arious hydrous or anhydroua types of finely porous silicon dioxide prefarabl~ having a large sur-face are understood`. Their inner surface should expediently be in the range of from 50 to 400 CD /g acGording to BET (Brunauer, Emmet and Teller)~ prefe~abl~ 150 to 300 cm2/g.
29 In goneral the silicic acld ha~ a ~ean partlcle size of '`, ' ~
~ ' . . :
~ E 73/F 264 1~5:1581~ ' ~
from 1 to 50 ~ . 1. :
By the addition of 9il~ CiC acid an~ ~ilo~ane oil the anti-ag~lomeration e~ect o~ hydrochloric acid is impro~ed, Such an addition i~ therefore preferr~d. In gen~ral 0.1 to 2 %, pre~erably 0.1 to 1 % by weight Or silieic acid in combination with 0.01 to 1.0, preferably 0.02 to 0.7 % by ~eight,of .~$10~ane oil, each tima caloulated on th~ low pressure poly-ethylene used, are su~ficisnt. The a~ount of ~ilicic acid and ~iloxane oil is not strictly limited, in 90me cases higher amounts may also be used, whereby the agglomeration inhibition 1~ further impro~ed but disa~vantages fo~ the blend with poly-vinyl chloride must be taken into consideration.
The organo-silicon compounds or sil~ana oils to be used aocording to the in~ention are liquid pol~iloxanes consicting f the recurring unit ~~1 - ~ :, -o-fi_ _ - ~
OR2 x - in which Rl and R2 each represents an alkyl radical preferably haYing from ~ to 6 carbon atom~,an aryl rad~c~l,preferably a phenyl or an aralkyl radical preferably ha~ing from 7 to 12 carbon atom~,and X is an integer of ~ro~ 10 to 1,OOO.The ~i5-cosity of the siloxane oils at Z~ C issuitably inthe ra~ ~ ~om ro to 500,000 centistokes, more suitably 500 to 50,000 centi-Jtokes. There are mentioned, by way of e~a~ple, dimethyl-, diethyl-, dipropyl-, methyl-ethyl-, dioc~y~-, dihèxyl-, me~hyl-propyl-, dibutyl- and didodeorl-poly~iloxan.es. ~ompounds o~
.29 the dimethyl-polyYiloxaIl~ series proved to ~e especially ad-- S - ' ,~
:. : . : : . : . . .
, : . . . ~ : - -: ~ .- - - . -~~ 73/F 264 51~80 ~ , vantageous. -The 9ilicic acid component and the polysiloxane, which are pos~ibly pre-mixed, are expediently added prlor to or at the beginning of the chlorination within a temperature interval in which the melting point o~ the polyethylene is not yet reached.
According to another mode of operation the ~ilicic acid is first added alone and the siloxane oi7 is then admixed during the course of chlorination. A pos~ible ~light agglomeration can be counter-acted at least partially by the later addition of siloxane oil, even if it is made prior to drying.
It i9 also possible, o~ course, to add the intended amount of qiloxane oil in portions during ~ome or all process steps.
Tha thermoplastic composition according to the invention may additionally contain known PVC ~tabilizers, ~or example barium or cadmium laurate, epoxide stabiliz~r~, organic phos- ;
phiteq, tin or lead compounds, as well as ~ther known additi~es.
for example W absorbers, lubricants, prnoes9ing auxiliaries, dyes and pigments.
Depending on the proportion o~ chlor~nated low pressure polyeth~lene, the thermoplastie compo~itiqn o~ the in~-ention e~n be used for making pipes, profiles, plate~, sheets, cables, fle~ible tubes~in~ection moulded articles and other shaped structures. Owing to the uniform ~ineness o~ the grain,~the composition can be easily prooessed by the dry blend technique.
Mi~ing of the component9 in the plasticize~ ~tate i9 not required.
To characterize the chlorinated low pressure polyethylenes to be uqed according to the in~ention the following met~ods were u~ed:
29 1) Residue Yalue accordlng to the tolue~e~acetone (TAC) method:
~ _ 7 _ '.' ' - '-: ' ' ' ' ` ` , ' .,' ~
:'~ " ~' .' ~ . . . - : ' . .. . ..
~ HOE 7~ 264 --` lOSle~
4 grams of the chloropolyeth~ylene to be te~ted were re-fluxed for 1 hour in 100 ml of a 1 : 1 mixture o~
toluene and acetone. The amount of i~soluble re~idue consisting of insufficiently chlorinated portions is a measurement for the through chlorination of the poly-ethylene particles. The smaller the residue the better the chlorination product is suitable for the compositions of the invention. I -2) Swelling value in methylcyclohexane (MCH)-The increase in weight of a sample after a 24 hour storage in methylcyclohexane is a ~urther measurement for the through chlorination of the polyethylene particles.
Portions which have not been chlorinated to a sufficient extent ~well very little. Products having a high swelling value are e~pecially ~uitable.
The ~ollowing examples illustrate the invention.
.
The chloropolyethylene used was prep~red as follows:
In a chlorination vessel 100 parts by~ weight of low pressure polyethylene having a reduced specific vi~c09ity of 1.3 dl/~, in 900 part~ by weight of 20 ~ hydrochloric acid were chlorin-ated, first at 80C until a chlorine cont~t of 28 ~ by weight had been reached and then at 121.5C to a ~inal chlorine ' content of 39.2 % by weight.
The product had a TAC value of 13 ~ and a MCH value of 14 %.
A mixture of 10 part~ b~ waight o~ the abo~e chlorination product and 90 parts b~ weight of suspen~ion pol~vinyl chloride 29 having a K value o~ 70 was rolled for 10 ~inutes at 175C with '':` . ' ~ '` ` . `' ' ''.~ ', ' ''' ,':' ' ':
EOE 73/~ 264 S~SE~Q
the addition of 3 part~ by weight Or barium/cadmium stabilizer and 1 part by weight of diphenyl-Octyl ph~phite. The plates moulded from the blend had the ~oll~wing ~alues Notched impact strength acoording t~ DIN 53,453 41.7 cm g/cm2 Impact strength at -20C according to D~N 53,453 "without break"
Notched tensile impact strength (DI~ 53,4~8) 197 cmkg/cm COMPARATIVE EXAMPLE
The same low pressure polyethylene was chlorinated under the conditions specified above~ but in wa~er without additio~
of hydrochloric acid. The polymer agglomerated to a large extent 90 that further ch~rination Wa9 much impeded. A chlorin-ation product was obtained having a chlorine contentlof 39.1 ~ ~`
by weight, a TAC value of 45 ~ and a MC~ valua of 3 ~. A b1end of 10 % by weight of the said chlorinati~n prod~ct with 90 by weight of suspension polyvinyl chloride having a K value of 70, prepared under the conditions of Example 1, was found to have a notched impact strength of 19.2 cmkg~cm and an impact strength at -20 C "without ~reak", according to DIN 53,453, and a notched ten~ile impact strength of 102 cmkg/cm~
according to DIN 53,448.
E X A M P L E 2: `
In a chl~ination vessel 100 parts b~ weight of low pressure polyethylene having a reduced specif~c ~iscosity of 1.2 dl/g in 1200 parts by weight of 24 ~ hydrochloric acid to which o.48 part by weight of silicic acid havi~g a ~e~ particle size of 12 ~m and an inner surfacQ v~ 200 cm2/g (~ET) and o.o48 part by weight of siloxane oil having a visco~ity of 1,000 centi-stokes at 25 C had been added, were chlcrinated,first at 80 C
29 to a chlorine content of 20 ~ by weightj then the temperature 9 _ :
: :: - , ., : : .: . ~ . :
. .
HOE _73/F 264 S~i8~ ' was rai4ed to 122C and chlorination wa.4 continued until a chlorine content of 6.6 ~ by weight was reached. The product had a TAC value of 33 ~ and a MCH value o~ 16 %.
A blend of 10 part3 of the chloropolyethylene obtained with 90 parts of suspen~qion PVC having a K value of 70, pre-pared under the conditions specified in E~ample 1, had a notched impact strength of 38.9 cmkg/cm and an impact strength at -20 C "without break".
_ X A M P L E 3:
In a chlorination vessel 100 parts by weight of low pre~sure polyethylene having a reduced specific viocosity of
~ ~ . -- - : . :
- ' : . : ~ :' ~OE 73/F 264 ~(~5~5~ilV ~ ' by weight of a i~iloxane oil, the p~rcentag0s being calculated on the starting polyethylene~ at a chlorinatlon temperature o~
from 50 *o 130C, the low presiqure polyethylene being possibly thermally treated or prssintered at a temperature in the range o~ from 100C~-i~ cryAtallite melting point and at least 10 %
of the chlorine being incorporated at a temperature of from 120 to 130C~
The thermoplastic composition consists of 98 to j50 % by weight pre~erably 95to 80 % by weigh*,of polyvinyl chloride or a copolymer o~ vinyl chloride with other comonomers, such as vinyl acetate acrylic acid esters or methacrylic acid esters, the amount o~ comonomer units in the polymer being at most 20 by weight, preferably 1 to 5 % by weight. The K value o~ the polymer is expediently in a ranga o~ from 50 to 80.
The remainlng ~ to 50 % by weight, pr~ferably 2 to 20 ~ by ~`
weight o~ the thermoplastic composition of the invention consists of a chlorinated low pressure polyethylene o~ high molecular weight containing 25 to 42 % by weight, p~ferably 30 to 40 $
by weight,o~ chlorine. The distribution o~ the chlorine atomes ~;
2n in the polyethylene grains, i.e. the degr~e of "pen~rating or through chlorination" iq oharacterizèd by the reisidue value according to the toluene/acetone method and the swelling value ~ ;
in methylcyclohexan~. The chlorinated low ~resqure polyethylene suitable for making the compositions of the invention shall have a residue value of 2 to 40 ~, pre~erably 2 to 30 %, and a swel-llng value of 10 to 70 %, pre~erably 20 to 50 %. ~oreover, it shall have a reduced specific viscosity o~ 1 to 5 dl/g, pre-~erably 1 to ~.5 dljg.
29 The chlorinated low pre~ure polyethylene o~ high molecular .
:: . :` . `~ .:. `. ` --~: ` - ` ` ' ` . ` , ,, .:
~:" ` ` :'. `, . . `, , , ~
-" ~0515~0.
~eight is fins-grainQd and-can readily b~ mi~ed homogeneously with the ~inyl chloride polymer powder.
The chlorinated low pressure polyethylene to be used according to the invention is produced ~y chlorinatin~ ~ne-grained low pressure polyethylene, ~hich may have been therm-ally treated or pre-sintered for 5 to 300 minutes at a temper-ature of from 100 C to its crystallite melting point (cf.German Offenlegungsschrift 1,720,800), in hydrochloric acid expedi-`ently 3 to 30 times the amount of acid is used, referred to the low pressure polyethylene. The chlorination is started at a temperature of from 50 to 100C and terminated at 120 to 130C.
The chlorination is advantageously started in a temper-ature range of from 70 to 90C, continued with continual temperature increase and terminated at ~ t~mperature ranging from 120 to l30 C, Alternati~ely, the chlorination can be effected in two steps, i.e, it is started at a temperature of from 50C to 100 C, the chlorine supply is interrupted while the temperature is raised to 120 to 130C and the chlorination i9 then conti~ued and terminated at that temperature.
The low pressure polyethylene used as starting material ha~ a reduced specific viscosity of 1 to ~ dl/g, preferably 1 to 3.5 dl/g-By silicic acid present in the chlo~ination as agglomer-ation inhibitor the ~arious hydrous or anhydroua types of finely porous silicon dioxide prefarabl~ having a large sur-face are understood`. Their inner surface should expediently be in the range of from 50 to 400 CD /g acGording to BET (Brunauer, Emmet and Teller)~ prefe~abl~ 150 to 300 cm2/g.
29 In goneral the silicic acld ha~ a ~ean partlcle size of '`, ' ~
~ ' . . :
~ E 73/F 264 1~5:1581~ ' ~
from 1 to 50 ~ . 1. :
By the addition of 9il~ CiC acid an~ ~ilo~ane oil the anti-ag~lomeration e~ect o~ hydrochloric acid is impro~ed, Such an addition i~ therefore preferr~d. In gen~ral 0.1 to 2 %, pre~erably 0.1 to 1 % by weight Or silieic acid in combination with 0.01 to 1.0, preferably 0.02 to 0.7 % by ~eight,of .~$10~ane oil, each tima caloulated on th~ low pressure poly-ethylene used, are su~ficisnt. The a~ount of ~ilicic acid and ~iloxane oil is not strictly limited, in 90me cases higher amounts may also be used, whereby the agglomeration inhibition 1~ further impro~ed but disa~vantages fo~ the blend with poly-vinyl chloride must be taken into consideration.
The organo-silicon compounds or sil~ana oils to be used aocording to the in~ention are liquid pol~iloxanes consicting f the recurring unit ~~1 - ~ :, -o-fi_ _ - ~
OR2 x - in which Rl and R2 each represents an alkyl radical preferably haYing from ~ to 6 carbon atom~,an aryl rad~c~l,preferably a phenyl or an aralkyl radical preferably ha~ing from 7 to 12 carbon atom~,and X is an integer of ~ro~ 10 to 1,OOO.The ~i5-cosity of the siloxane oils at Z~ C issuitably inthe ra~ ~ ~om ro to 500,000 centistokes, more suitably 500 to 50,000 centi-Jtokes. There are mentioned, by way of e~a~ple, dimethyl-, diethyl-, dipropyl-, methyl-ethyl-, dioc~y~-, dihèxyl-, me~hyl-propyl-, dibutyl- and didodeorl-poly~iloxan.es. ~ompounds o~
.29 the dimethyl-polyYiloxaIl~ series proved to ~e especially ad-- S - ' ,~
:. : . : : . : . . .
, : . . . ~ : - -: ~ .- - - . -~~ 73/F 264 51~80 ~ , vantageous. -The 9ilicic acid component and the polysiloxane, which are pos~ibly pre-mixed, are expediently added prlor to or at the beginning of the chlorination within a temperature interval in which the melting point o~ the polyethylene is not yet reached.
According to another mode of operation the ~ilicic acid is first added alone and the siloxane oi7 is then admixed during the course of chlorination. A pos~ible ~light agglomeration can be counter-acted at least partially by the later addition of siloxane oil, even if it is made prior to drying.
It i9 also possible, o~ course, to add the intended amount of qiloxane oil in portions during ~ome or all process steps.
Tha thermoplastic composition according to the invention may additionally contain known PVC ~tabilizers, ~or example barium or cadmium laurate, epoxide stabiliz~r~, organic phos- ;
phiteq, tin or lead compounds, as well as ~ther known additi~es.
for example W absorbers, lubricants, prnoes9ing auxiliaries, dyes and pigments.
Depending on the proportion o~ chlor~nated low pressure polyeth~lene, the thermoplastie compo~itiqn o~ the in~-ention e~n be used for making pipes, profiles, plate~, sheets, cables, fle~ible tubes~in~ection moulded articles and other shaped structures. Owing to the uniform ~ineness o~ the grain,~the composition can be easily prooessed by the dry blend technique.
Mi~ing of the component9 in the plasticize~ ~tate i9 not required.
To characterize the chlorinated low pressure polyethylenes to be uqed according to the in~ention the following met~ods were u~ed:
29 1) Residue Yalue accordlng to the tolue~e~acetone (TAC) method:
~ _ 7 _ '.' ' - '-: ' ' ' ' ` ` , ' .,' ~
:'~ " ~' .' ~ . . . - : ' . .. . ..
~ HOE 7~ 264 --` lOSle~
4 grams of the chloropolyeth~ylene to be te~ted were re-fluxed for 1 hour in 100 ml of a 1 : 1 mixture o~
toluene and acetone. The amount of i~soluble re~idue consisting of insufficiently chlorinated portions is a measurement for the through chlorination of the poly-ethylene particles. The smaller the residue the better the chlorination product is suitable for the compositions of the invention. I -2) Swelling value in methylcyclohexane (MCH)-The increase in weight of a sample after a 24 hour storage in methylcyclohexane is a ~urther measurement for the through chlorination of the polyethylene particles.
Portions which have not been chlorinated to a sufficient extent ~well very little. Products having a high swelling value are e~pecially ~uitable.
The ~ollowing examples illustrate the invention.
.
The chloropolyethylene used was prep~red as follows:
In a chlorination vessel 100 parts by~ weight of low pressure polyethylene having a reduced specific vi~c09ity of 1.3 dl/~, in 900 part~ by weight of 20 ~ hydrochloric acid were chlorin-ated, first at 80C until a chlorine cont~t of 28 ~ by weight had been reached and then at 121.5C to a ~inal chlorine ' content of 39.2 % by weight.
The product had a TAC value of 13 ~ and a MCH value of 14 %.
A mixture of 10 part~ b~ waight o~ the abo~e chlorination product and 90 parts b~ weight of suspen~ion pol~vinyl chloride 29 having a K value o~ 70 was rolled for 10 ~inutes at 175C with '':` . ' ~ '` ` . `' ' ''.~ ', ' ''' ,':' ' ':
EOE 73/~ 264 S~SE~Q
the addition of 3 part~ by weight Or barium/cadmium stabilizer and 1 part by weight of diphenyl-Octyl ph~phite. The plates moulded from the blend had the ~oll~wing ~alues Notched impact strength acoording t~ DIN 53,453 41.7 cm g/cm2 Impact strength at -20C according to D~N 53,453 "without break"
Notched tensile impact strength (DI~ 53,4~8) 197 cmkg/cm COMPARATIVE EXAMPLE
The same low pressure polyethylene was chlorinated under the conditions specified above~ but in wa~er without additio~
of hydrochloric acid. The polymer agglomerated to a large extent 90 that further ch~rination Wa9 much impeded. A chlorin-ation product was obtained having a chlorine contentlof 39.1 ~ ~`
by weight, a TAC value of 45 ~ and a MC~ valua of 3 ~. A b1end of 10 % by weight of the said chlorinati~n prod~ct with 90 by weight of suspension polyvinyl chloride having a K value of 70, prepared under the conditions of Example 1, was found to have a notched impact strength of 19.2 cmkg~cm and an impact strength at -20 C "without ~reak", according to DIN 53,453, and a notched ten~ile impact strength of 102 cmkg/cm~
according to DIN 53,448.
E X A M P L E 2: `
In a chl~ination vessel 100 parts b~ weight of low pressure polyethylene having a reduced specif~c ~iscosity of 1.2 dl/g in 1200 parts by weight of 24 ~ hydrochloric acid to which o.48 part by weight of silicic acid havi~g a ~e~ particle size of 12 ~m and an inner surfacQ v~ 200 cm2/g (~ET) and o.o48 part by weight of siloxane oil having a visco~ity of 1,000 centi-stokes at 25 C had been added, were chlcrinated,first at 80 C
29 to a chlorine content of 20 ~ by weightj then the temperature 9 _ :
: :: - , ., : : .: . ~ . :
. .
HOE _73/F 264 S~i8~ ' was rai4ed to 122C and chlorination wa.4 continued until a chlorine content of 6.6 ~ by weight was reached. The product had a TAC value of 33 ~ and a MCH value o~ 16 %.
A blend of 10 part3 of the chloropolyethylene obtained with 90 parts of suspen~qion PVC having a K value of 70, pre-pared under the conditions specified in E~ample 1, had a notched impact strength of 38.9 cmkg/cm and an impact strength at -20 C "without break".
_ X A M P L E 3:
In a chlorination vessel 100 parts by weight of low pre~sure polyethylene having a reduced specific viocosity of
3.5 dl/g in 1,000 part_ by weight of 20 ~ by weight h-~drochloric acid were chlorinated first at 70 C to a chlorinQ content of 20 % by weight, then the tempQraturQ was rais~d to 126C and chlorination was continued to a final chlorine c~ntent of 36.3 %
by weight. ThQ product obtained had a TAC value of 15 ~ and a MCH value of 21 %.
A blend of tO parts by weight of the chloropolyethylene with 90 parts by weight of suqpenRlon P~C having a K value of 70, prepared according to claim 1~ had a notched impact strength of 51.3 cmkg/cm and an impàct strength at -20C "without break".
:................... . . . - ~ .... : .
by weight. ThQ product obtained had a TAC value of 15 ~ and a MCH value of 21 %.
A blend of tO parts by weight of the chloropolyethylene with 90 parts by weight of suqpenRlon P~C having a K value of 70, prepared according to claim 1~ had a notched impact strength of 51.3 cmkg/cm and an impàct strength at -20C "without break".
:................... . . . - ~ .... : .
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A thermoplastic composition consisting essentially of a) 98 to 50% by weight of a vinyl chloride polymer and b) 2 to 50% by weight of a chlorinated low pressure poly-ethylene having a chlorine content of 25 to 42% by weight, a reduced specific viscosity of 1 to 5 dl/g, a residue value of 2 to 40%, measured by extraction in a 1 : 1 mixture of toluene and acetone, and a swelling value of 10 to 70 %, measured in methylcyclohexane, the chlorinated polyethylene being prepared by chlorination of low pressure polyethylene in aqueous hydrochloric acid of 10 to 35 % strength by weight in the presence of 0 to 2 % by weight of silicic acid and 0 to 1.0 % by weight of siloxane oil, the percentages being calculated on the polyethylene, consisting of the recurring unit wherein R1 and R2 each represent an alkyl radical, an aryl radical, a phenyl or an aralkyl radical and x is an integer of from 10 to 1,000, at a chlorination temperature of from 50 to 130°C, at least 10 % by weight of the chlorine being incorporated at a temperature of from 120 to 130°C.
2. A thermoplastic composition as claimed in claim 1, in which the chlorinated polyethylene was prepared by chlorination starting at 50 to 100°C and ending at 120 to 130°C.
3. A thermoplastic composition as claimed in claim 1, in which the chlorinated polyethylene was prepared by chlorination starting at 70 to 90°C and ending at 120 to 130°C.
4. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3, in which the chlorinated polyethylene has a chlorine content of from 30 to 40%.
5. A thermoplastic composition as claimed in claim 1 claim 2 or claim 3, in which the chlorinated polyethylene was prepared from low pressure polyethylene which has been thermally treated or presintered at a temperature in the range of from 100°C to its crystallite melting point.
6. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3 in which the vinyl chloride polymer is poly-vinyl chloride.
7. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3 in which the vinyl chloride polymer is a co-polymer of vinyl chloride with 0.01 to 20% by weight of another monomer selected from the group of vinyl acetate, acrylic acid esters and methacrylic acid esters.
8. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3, in which the vinyl chloride polymer is a co-polymer of vinyl chloride with 1 to 5 % of a monomer selected from the group of vinyl acetate, acrylic acid esters and meth-acrylic acid esters.
9. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3, in which the viscosity number of siloxane oil is in the range from 1000 to 500,000 centistokes.
10. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3 in which the quantity of silicic acid is from 0.1 to 1 % by weight.
11. A thermoplastic composition as claimed in claim 1, claim 2 or claim 3, in which the silicic acid has an average particle size of from 1 to 50 µm and an inner surface of from 50 to 4002cm /g (according to BET).
12. A process for the preparation of a thermoplastic composition in which a) 98 to 50 % by weight of a vinyl chloride polymer is mixed with b) 2 to 50 % by weight of chlorinated low pressure poly-ethylene having a chlorine wherein the polyethylene has a chlorine content of 25 to 42 % by weight, a reduced specific viscosity of 1 to 5 dl/g, a residue value of 2 to 40 %, measured by extraction in a 1 : 1 mixture of toluene and acetone, and a swelling value of 10 to 70 %, measured in methylcyclohexane, and is prepared by chlorination in hydrochloric acid of 10 to 30 % strength by weight in the presence of 0 to 2 %
by weight of silicic acid and 0 to 1.0 % by weight of siloxane oil, consisting of the recurring unit wherein R1 and R2 each represent an alkyl radical, an aryl radical, a phenyl or an aralkyl radical and x is an integer of from 10 to 1,000, the percentages being calculated on the polyethylene, at a chlori-nation temperature of from 50 to 130°C, at least 10 %
by weight of the chlorine being incorporated at a temperature of from 120 to 130°C.
by weight of silicic acid and 0 to 1.0 % by weight of siloxane oil, consisting of the recurring unit wherein R1 and R2 each represent an alkyl radical, an aryl radical, a phenyl or an aralkyl radical and x is an integer of from 10 to 1,000, the percentages being calculated on the polyethylene, at a chlori-nation temperature of from 50 to 130°C, at least 10 %
by weight of the chlorine being incorporated at a temperature of from 120 to 130°C.
13. A process for the preparation of a thermoplastic composition as claimed in claim 12 in which the viscosity number of the siloxane oil is in the range of from 1000 to 500,000 centistokes.
14. A process for the preparation of a thermoplastic composition as claimed in claim 12 in which the quantity of silicic acid is from 0.1 to 1 % by weight.
15. A process for the preparation of a thermoplastic composition as claimed in claim 12, claim 13 or claim 14 in which the silicic acid has an average particle size of from 1 to 50 µm and a inner surface of from 50 to 400 cm2/g (according to BET).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2343982A DE2343982C3 (en) | 1973-08-31 | 1973-08-31 | Thermoplastic mass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051580A true CA1051580A (en) | 1979-03-27 |
Family
ID=5891279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA207,124A Expired CA1051580A (en) | 1973-08-31 | 1974-08-15 | Thermoplastic composition consisting of a vinyl chloride polymer and a chlorinated low pressure polyethylene |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5727912B2 (en) |
| AT (1) | AT329269B (en) |
| BE (1) | BE819448A (en) |
| CA (1) | CA1051580A (en) |
| CH (1) | CH598313A5 (en) |
| DE (1) | DE2343982C3 (en) |
| FR (1) | FR2242431B1 (en) |
| GB (1) | GB1475716A (en) |
| IL (1) | IL45558A (en) |
| IT (1) | IT1020309B (en) |
| NL (1) | NL7411333A (en) |
| SE (1) | SE394447B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55110145A (en) * | 1979-02-14 | 1980-08-25 | Stauffer Chemical Co | Film forming composition |
| DE2914463A1 (en) * | 1979-04-10 | 1980-10-23 | Hoechst Ag | MEDICAL DEVICES FOR PARENTERAL LIQUIDS |
| DE2937178A1 (en) * | 1979-09-14 | 1981-04-02 | Hoechst Ag, 6000 Frankfurt | THERMOPLASTIC MASS |
| JPH042979Y2 (en) * | 1987-04-22 | 1992-01-31 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1275717A (en) * | 1970-02-09 | 1972-05-24 | Ici Ltd | Chlorination of polyethylene |
-
1973
- 1973-08-31 DE DE2343982A patent/DE2343982C3/en not_active Expired
-
1974
- 1974-08-15 CA CA207,124A patent/CA1051580A/en not_active Expired
- 1974-08-26 NL NL7411333A patent/NL7411333A/en not_active Application Discontinuation
- 1974-08-27 IL IL45558A patent/IL45558A/en unknown
- 1974-08-28 CH CH1174574A patent/CH598313A5/xx not_active IP Right Cessation
- 1974-08-29 IT IT26751/74A patent/IT1020309B/en active
- 1974-08-29 GB GB3786374A patent/GB1475716A/en not_active Expired
- 1974-08-30 SE SE7411022A patent/SE394447B/en unknown
- 1974-08-30 AT AT705174A patent/AT329269B/en not_active IP Right Cessation
- 1974-08-30 FR FR7429631A patent/FR2242431B1/fr not_active Expired
- 1974-08-30 JP JP9903874A patent/JPS5727912B2/ja not_active Expired
- 1974-09-02 BE BE148131A patent/BE819448A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL45558A (en) | 1977-06-30 |
| GB1475716A (en) | 1977-06-01 |
| DE2343982C3 (en) | 1979-08-09 |
| ATA705174A (en) | 1975-07-15 |
| JPS5064348A (en) | 1975-05-31 |
| NL7411333A (en) | 1975-03-04 |
| FR2242431B1 (en) | 1978-02-17 |
| DE2343982B2 (en) | 1978-12-07 |
| CH598313A5 (en) | 1978-04-28 |
| DE2343982A1 (en) | 1975-03-13 |
| BE819448A (en) | 1975-03-03 |
| JPS5727912B2 (en) | 1982-06-14 |
| SE7411022L (en) | 1975-03-03 |
| FR2242431A1 (en) | 1975-03-28 |
| IT1020309B (en) | 1977-12-20 |
| SE394447B (en) | 1977-06-27 |
| IL45558A0 (en) | 1974-11-29 |
| AT329269B (en) | 1976-05-10 |
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