CA1040334A - Lubricants for the processing of plastic materials - Google Patents
Lubricants for the processing of plastic materialsInfo
- Publication number
- CA1040334A CA1040334A CA238,819A CA238819A CA1040334A CA 1040334 A CA1040334 A CA 1040334A CA 238819 A CA238819 A CA 238819A CA 1040334 A CA1040334 A CA 1040334A
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- Canada
- Prior art keywords
- wax
- waxes
- lubricant
- saponification
- partial
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
LUBRICANTS FOR THE PROCESSING OF PLASTIC MATERIALS
Abstract of the disclosure:
By extraction with aliphatic hydrocarbons, waxes having a light color are obtained from tree-barks, which waxes may be oxidized, saponified, esterified or amidated. These waxes and their derivatives are suitable as lubricants for plastic materials, especially poly(vinyl chloride). They may also be used in admixture with other waxes, for example natural or hydrocarbon waxes or the derivatives thereof.
Abstract of the disclosure:
By extraction with aliphatic hydrocarbons, waxes having a light color are obtained from tree-barks, which waxes may be oxidized, saponified, esterified or amidated. These waxes and their derivatives are suitable as lubricants for plastic materials, especially poly(vinyl chloride). They may also be used in admixture with other waxes, for example natural or hydrocarbon waxes or the derivatives thereof.
Description
HOE 74/F 80~
104~)334 The present ~nvention relates to lubricants for the proces-slng of plastic materials.
By extraction with solvents, waxes may be obtained from tree-barks, for examplé by mean-~ of a ~olvent mixture of ali-ph~tio and srQma+ic hydrocarbo~Q (U.S. Po+~n+ ~o. 3,7Qg~Q58) This latter wax is distinguished with respect to its composi-tion and its properties from bark waxes obtained by extractlon i with other solvents, and it may be used for mang applications for which the other bark waxes cannot be employed. Among others, an application as internal iubricant for the process~ng o~ pla~tic materials is described for the bark wax of the cited U.S. Patent. However, the wax has a brown-green to dark-green , . . .
~, color which is disadvantageous for its use as lubricant since lt causes discoloration Or the plastic articles manufactured with addition of this wax. In many cases therefore, the use o~ thls bark wax as lubricant for the processing of plastic materials must be excluded from the start.
It 18 known for a certaln time to obtain from tree-barks also a light yellow to light brown wax having a composition dlffering from that of the abovementioned w~x by using purely aliphatic hydrocarbons for the extractlon of the barks (U.S.
¦ Patent No. 2,662,893).
It has now been fond that this wax obtained by extraction ! of barks with aliphatic hydrocarbons may be used ~er se as well as ln the form of modification products and mixtures with other wax-llke substances as lubricant for the processing Or plastic material~.
The present invention provide~ therefore a pla~tic compo~
sition containin~ a lubricant, which comprises as lubricant a ~0 wax obtained by extraction of tree-barks with an allphatic , - 2 -~ - . -.;:
;'`
;' ~: . ` ' ' :
'. .'. ' ~, ' .'., '. ' - . ' .
~OE 74/F 809 ~04~334 hydrocarbon and having an acid number of from 20 to 90, a sapo-i nlfication number of from 110 to 180 snd a melting point of from 45 to 70C in an amount of from 0.1 to 5% by weight, rela-ti~e to the plastic composition.
The essential feature of the ~n~entlon is tne use of bark wax obtained by extractlon of tree-barks with aliphatic hydro-carbons, the oxidates or refined products thereof, or the esteri-fication,-saponification, partial esterification, partial sapo-nification or amidation products of the bark wax or of the oxi-dates or refined products thereof, as lubricant for the proces-sing of plastic materials, optlonally ln admixture with other i natural waxes and/or hydrocarbon waxes, with oxidates or re-fined products of other natural or hydrocarbon waxes or the esterification, saponification, partlal esterification, partial saponification or amidation products oi the natural waxes, the oxidized natural waxes or the h~drocarbon waxes.
It was surprising and not to be expected that the wax ex-tracted from tree-barks by means of purely aliphatic hydrocar bons has a good lubrlcating effect in the processing of plastic materials, since accordlng to the present knowledge and the teaching of U.S. Patent No. 3,789,058 it had to be supposed that such results were obtained only with the use of a wax extracted by means of a mixture of aliphatic and aromatic hydrocarbons because of its special composition. All the less could be expected the bark wax obtained with the use of ali-phatic hydrocarbons tb be an even better lubricant than the wax obtained by extraction with the mixture of~liphatics and aromatics and especially recommended for this purpose.
29 Suitable waxes for the applicatlon as lubricant in accor-, . ~
~.. ,~ .. .... .. . .. .. . . .
I~OE 74/F 809 ~ 1~)4~334 dance with the present invention ~L-e those obtained by extraction of tree-barks with aliphatic hydrocarbons including cycloparaffins, for example hexane, heptane, petroleum or naphtha. The preparation of such waxes is described in U.S. Patent No . 2, 662, 893 . The waxes are light yellow to light brown substances of beeswax-like consistency which have acid numbers of from 20 to 90, saponification numbers of from 110 to 180 and melting points of from 45 to 70C. They have a lower content of phenolic compounds than the waxes extracted from barks by means of mixtures of aliphatic and aromatic hydrocarbons. .
Before their application according to this invention, the bark waxes may be specially refined, purified or brightened to a further extent, for example by extraction with solvents or reprecipitation from solvents or solvent mixtures, or by treatment with active charcoal or bleaching earths. A further brightening can be obtained also by means of usual bleaching agents. Modiication products of the bark wax, for example esterification, saponification, partial esterification, partial saponification, or amidation products, may also be used, which are obtained for example by reaction according to known processes of a bark wax melt with mono-or polyvalent aliphatic alcohols having from 2 to about 30, preferably from 2 to 6 carbon atoms, or with mono- to trivalent metal ions, the wax being entirely or partially esterified or saponified, or partially esterified in a first step and partially or entirely saponified in a subsequent second step. In this process, besides the free acids of the waxes also the bound acids can be reacted after a previous ester cleavage. Amidation products are obtained in 29 corresponding manner by reaction of the waxes with mono- or ~ ~ 4 ~
0~ 334 poly~alent aliphatic amines or ammonla. As esterification components, there may be used for example ethanol, propanol, butanol, stear~l alcohol or montanol (hydrogenated montan wax), furthermore diols such as ethylene glycol, propanediol-(1,2), butanedlol-(1,3) or diethglenegi~iol, ~nd polyhydric alcohoi~
such a~ trimethylolpropane or pentaerythritol. Saponification components are above all metal ions of the tst, 2nd and 3rd group of the Periodic System, for example ~i+, Na+, K+, ~g2+, Ca2l, A13+, Pb2+ or Cd2~. Sultable su~stances for the amlda-tlon are for example ~m~nes such as ethylamine, stearylamine, ethylene dlamlne, as well as ammonla.
Accordlng to the ln~ention, up to 95% by weight of the bark wax or it~ modlflcation products may be replaced by other natural waxes and/or h~drocarbon waxes or the reflned products or oxldates thereof and the e~terlrlcatlon, saponlflcatlon, partl~l esterl~icatlon, partial saponlflcatlon or amldatlon pro-ducts prepared therefrom ln slmllar manner as the modlflcatlon products of the bark wax; that i~, lt ls posslble and in many c~ses even ad~antageous to use the bark wax or the modlflcatlon products thereof ln adm~xture with these waxes.
By other natural waxes, there are to be understood vege-table or anlmal waxes, ror example sugar cane wax, candelllla wax, ourlcury wax, carnauba wax and dereslnlfied or non-deresi-nl~ied crude montan wax. These natural waxes are sultable as cocomponents, especlally in the ~orm Or thelr reflned products obtàlned for example by treatment wlth aqueous chromosulrurlc acld or by other Xnown Purirlcation processes, which products are known as "partially synthetic waxesn. The refined products 29 are preferably used after ha~ing been converted to esterificatlon, _ 5 _ HO~ 74/F 809 1~4~334 saponification, partial esterification, partial saponification or amidation products known as "partially synthetic ester waxes", especially in the form of the reaction products of montan wax.
Hydrocarbon waxes suitable as cocomponents are natural or synthetic paraffin waxes, microcrystalline waxes and polyole-fines. By polyolefins there are to be understood preferably unhranched ~-olefins having from 16 to 70 carbon atoms in the molecule, for example those obtained by oligomerization 1 10 of ethylene in the presence of organo-aluminum catalysts, furthermore polyolefin waxes obtained by homo- or copolymeri-zation of ethylene and other -olefins, or by thermal, cata-lytic or oxidative degradation of high molecular weight poly-olefins. The hydrocarbon waxes may be oxidized with air and/
, 15 or other oxidation agents, for example chromosulfuric acid.
i Oxidized hydrocarbon waxes are for example also the products ! having an acid number of up to 200, which are obtained ac-cording to U.S. Patent No. 3,756,999 by air oxidation of high molecular weight polyolefins in aqueous dispersion, and which may be after-oxidized with aqueous chromosulfuric acid. The oxidized hydrocarbon waxes are preferably used in the form of their esterification, saponification, partial esterification, partial saponification or amidation products. The natural and hydrocarbon waxes or their derivatives may be used also as mixtures with each other or with themselves in any ratio.
The quantitative ratio of bark wax to cocomponents may be widely varied. Generally, it depends on the character of the q onents used and the kind of the lubrication effect intended, 29 that is, whether a more internal or more external lubricating ~.. . ... . . . . .
.. . : . ~ , .- - . , ~ . - .
" . .
1~4~ 334 effect is desired. Normally, the bark wax amount in the mix-A tures is from 5 to 95 welght %, preferably ~rom 20 to 80 weight and especially from 40 to 80 weight %.
The lubricant combinations are obtained for example by mixing the melts of the cocomponents in the desired ratio.
Another method which has proved to be especially advantageous ; for the preparation of lubricant combinatinns of modification products of bark wax and modification products of natural or hydrocarbon waxes consists in sub~ecting the starting mat~rlals to a common esterlficatlon, saponification~amidation, etc.
In the processing of plastic materials, especially PVC, the lubrlcants in accordance with this invention on the basis of waxes obtained from tree-barks by extraction with allphatic hydrocarbons dlsplay lmproved propertles as compared to the bark waxes hltherto used for this purpose. The waxes in accor-dance with thls invention have a dl~tinct internal lubricating i e~fe¢t, ~o that they are preferably employed ~or the manufac-ture o~ transparent plastlcs articles. Because of the llght I color of the waxes, their use, contrary to the bark wax hither-¦ 20 to known, does not result, or onlg to an lnslgnlflcant ex-¦ tent;in a discoloration of the plastic material, so that lt is now posslble to utilize bark wax whlch in prlnclple ls aval-lable in large amounts for thls purpose-The bark wax u~ed as processlng auxlliary for plastic materlals has a lubricating effect comparable to the most efficient ones of the hitherto known products, namely the wax acid derivatives, and its transparency is even ~ar more super-ior.
29 The lubricating propertles of the bark wax may be wldel~
~ ` ~oa~0334 varied and adapted to any requirements of the industrial prac-tice with the aid of other waxes and/or by conversion to the modification products such as esters, soaps etc. In this manner, for example, any desired gradation between a more inter-nal and a more external lubricating effect can be adjusted.
By using the cadmium or lead salts, a stabilizing effect may be additionally obtained.
The cited possibilities of modifying the lubricating pro-perties of the bark wax by mixing it with other waxes and/or conversion to reaction products may of course be transferred also to bark waxes obtained by different extraction methods, for example with solvent mixtures of aliphatic and aromatic I hydrocarbons. However, because of the different composition and the darker color of these waxes, the high quality of the wax extracted from barks with purely aliphatic hydrocarbons cannot be attained. The cited modifications improve also the properties of the bark waxes necessary for application in other fields, for example in polishing agents, in auxiliaries for the treatment of metals, in hydrophobizing and mold re-lease agents.
The lubricants in accordance with the present invention are added to the thermoplastic material in amounts of from O.I to 5.0%, preferably from 0.1 to 3.0%, relative to the weight of the plastic material, generally simultaneously with further additives usual in plastics processing, such as stabi-lizers, flow improving agents or dyestuffs.
The following examples illustrate the invention.
E X A M P L E 1:
29 A light yellow wax obtained from the bark of a douglas fir ~ 4033~ HOE 74/F 809 (pseudotsuga taxifolia) by extraction with heptane, and having an acid number of 65, a saponification number of 149 and a drop-ping point of 57C is used as lubricant for poly(vinyl chloride.) A mixture of i 5 100.0 parts by weight of suspension poly(vinyl chloride) hav-ing a K value of 65, 0.5 part by weight of bark wax and 1.0 part by weight of an organo-tin compound as stabilizer is processed at 180C on heated rolls. A rolling time of 70 minutes until decomposition is attained without sticking.
From a similar mixture, containing however 1.0 part of the bark wax and 1.5 parts of the stabilizer, rolled as in-dicated above, a plate having a thickness of 2 millimeters is molded. The plate is practically colorless it has a transpa-rency of 90% in a beam of light of a wave length of 741 nano-meters.
For a comparison, the bark wax is replaced by an ester wax on the basis of montan wax. The rolling time in this case is only 44 minutes and the transparency 2%.
E X A M P L E 2: (Comparative Example) A green-brown wax obtained by extraction from the bark of a douglas fir with a heptane/benzene mixture is tested as lubricant as described in Example 1. The rolling time is 69 minutes until decomposition, but the rough sheet starts to stick after 62 minutes already.
The plate manufactured for the transparency test has a transparency of 83%.
_ g _ :
E X A M P ~ E ~:
300 Grams of the bark wax used in Example 1 are saponified by stirring the melt at 110C with 11 grams of calcium hydroxide.
A wax soap is obtained having a residual acid number of 10, a ~aponification number of 120 and a dropping point of 87~C. The wax soap is tested as lubricant in the processing of poly-(~inyl chloride) according to Example 1. A rolling time of 77 minutes until decomposition ~sticking starts after 68 minu-tes) is attained. The manufacture of a test specimen for the transparency test gives a plate having a light color and a transparency of 89~.
E X A M P ~ E 4:
300 Crams of the bark was used in Example 1 in molten state are esterified at 110C with 90 grams of stearyl alcohol ln the presence of eatalytic amounts of sulfuric acld until a resldual acld number of 30 ls attained. The partial ester ob-talned has a saponlficatlon number of 130 and a dropplng point o~ 58&. The ester is used as lubrleant in the proeessing of ;' PVC as deseribed in Example 1. A rolling time of 73 mlnutes until stleking 18 attalned. The test specimen manufactured aeeording to Example 1 has a faintly yellow color, and it~
transparency is 92%.
E X A M P ~ E 5:
100 Grams of the bark wax used in Example 1 are mixed with 100 grams of an ester wax ~n the basis of montan wax hav-lng an acid number of 18 and a saponification number of 138 by stlrring the melts together at 110C. The wax mixture ob-talned is used according to Example 1 as lubricant for the 29 processing of poly(vinyl chloride). A rolling time of 60 minu-. -- 10 --~ '"' . ' ' ' ~ ' . ' ` ' ' ' ': ' ' ' ' ' '' ~ . . : , . ''.-.,, :,:, : -, , - ... ..
OE 74/~ 809 ,_ 104~334 -- tes untll ~ticking is attalned. The te~t specimen ~or measur-ing the transparency ha~ a yellowish color and it~ transparency 18 86~.
E X A M P ~ E 6:
; 120 Cram~ of tne ~arX wax u~ed in Exampl~ 1 ara mixed wlth 80 grams of a poly-ethylene oxldized wlth air and having an acid number of 65, a saponification number oi 110 and a dropping point of 110C (obtained according to the proces~ des-cribed in U.S. Patent No. 3,756,999 by air oxidation ln aque-OUQ dispersion from a high molecular weight pla~tic-like poly-eth~lene). The mixture iQ subsequently ~aponifled by ~tirring the melt with 8 grams of calcium hydroxide until a residual acld number of 5 i8 attained. A wax soap ha~ing a saponifi-cation number of 110 and a dropping point of 105C i~ obtalned.
j 15 U~ed as lubricant ~or the processing o~ poly(vinyl chloride) as ~ndicated in Example 1, a rolli~g timo o~ 75 minutes until stic~klng i_ attained. The test ~pecimen ~or the e~aluation o~ the tran~parency i8 practlcally colorless. The tranQparency 18 9~, . _ 11 -., . i- -.,, .. . . ..... . ., . -. ...... ... ... .. - . . . .
104~)334 The present ~nvention relates to lubricants for the proces-slng of plastic materials.
By extraction with solvents, waxes may be obtained from tree-barks, for examplé by mean-~ of a ~olvent mixture of ali-ph~tio and srQma+ic hydrocarbo~Q (U.S. Po+~n+ ~o. 3,7Qg~Q58) This latter wax is distinguished with respect to its composi-tion and its properties from bark waxes obtained by extractlon i with other solvents, and it may be used for mang applications for which the other bark waxes cannot be employed. Among others, an application as internal iubricant for the process~ng o~ pla~tic materials is described for the bark wax of the cited U.S. Patent. However, the wax has a brown-green to dark-green , . . .
~, color which is disadvantageous for its use as lubricant since lt causes discoloration Or the plastic articles manufactured with addition of this wax. In many cases therefore, the use o~ thls bark wax as lubricant for the processing of plastic materials must be excluded from the start.
It 18 known for a certaln time to obtain from tree-barks also a light yellow to light brown wax having a composition dlffering from that of the abovementioned w~x by using purely aliphatic hydrocarbons for the extractlon of the barks (U.S.
¦ Patent No. 2,662,893).
It has now been fond that this wax obtained by extraction ! of barks with aliphatic hydrocarbons may be used ~er se as well as ln the form of modification products and mixtures with other wax-llke substances as lubricant for the processing Or plastic material~.
The present invention provide~ therefore a pla~tic compo~
sition containin~ a lubricant, which comprises as lubricant a ~0 wax obtained by extraction of tree-barks with an allphatic , - 2 -~ - . -.;:
;'`
;' ~: . ` ' ' :
'. .'. ' ~, ' .'., '. ' - . ' .
~OE 74/F 809 ~04~334 hydrocarbon and having an acid number of from 20 to 90, a sapo-i nlfication number of from 110 to 180 snd a melting point of from 45 to 70C in an amount of from 0.1 to 5% by weight, rela-ti~e to the plastic composition.
The essential feature of the ~n~entlon is tne use of bark wax obtained by extractlon of tree-barks with aliphatic hydro-carbons, the oxidates or refined products thereof, or the esteri-fication,-saponification, partial esterification, partial sapo-nification or amidation products of the bark wax or of the oxi-dates or refined products thereof, as lubricant for the proces-sing of plastic materials, optlonally ln admixture with other i natural waxes and/or hydrocarbon waxes, with oxidates or re-fined products of other natural or hydrocarbon waxes or the esterification, saponification, partlal esterification, partial saponification or amidation products oi the natural waxes, the oxidized natural waxes or the h~drocarbon waxes.
It was surprising and not to be expected that the wax ex-tracted from tree-barks by means of purely aliphatic hydrocar bons has a good lubrlcating effect in the processing of plastic materials, since accordlng to the present knowledge and the teaching of U.S. Patent No. 3,789,058 it had to be supposed that such results were obtained only with the use of a wax extracted by means of a mixture of aliphatic and aromatic hydrocarbons because of its special composition. All the less could be expected the bark wax obtained with the use of ali-phatic hydrocarbons tb be an even better lubricant than the wax obtained by extraction with the mixture of~liphatics and aromatics and especially recommended for this purpose.
29 Suitable waxes for the applicatlon as lubricant in accor-, . ~
~.. ,~ .. .... .. . .. .. . . .
I~OE 74/F 809 ~ 1~)4~334 dance with the present invention ~L-e those obtained by extraction of tree-barks with aliphatic hydrocarbons including cycloparaffins, for example hexane, heptane, petroleum or naphtha. The preparation of such waxes is described in U.S. Patent No . 2, 662, 893 . The waxes are light yellow to light brown substances of beeswax-like consistency which have acid numbers of from 20 to 90, saponification numbers of from 110 to 180 and melting points of from 45 to 70C. They have a lower content of phenolic compounds than the waxes extracted from barks by means of mixtures of aliphatic and aromatic hydrocarbons. .
Before their application according to this invention, the bark waxes may be specially refined, purified or brightened to a further extent, for example by extraction with solvents or reprecipitation from solvents or solvent mixtures, or by treatment with active charcoal or bleaching earths. A further brightening can be obtained also by means of usual bleaching agents. Modiication products of the bark wax, for example esterification, saponification, partial esterification, partial saponification, or amidation products, may also be used, which are obtained for example by reaction according to known processes of a bark wax melt with mono-or polyvalent aliphatic alcohols having from 2 to about 30, preferably from 2 to 6 carbon atoms, or with mono- to trivalent metal ions, the wax being entirely or partially esterified or saponified, or partially esterified in a first step and partially or entirely saponified in a subsequent second step. In this process, besides the free acids of the waxes also the bound acids can be reacted after a previous ester cleavage. Amidation products are obtained in 29 corresponding manner by reaction of the waxes with mono- or ~ ~ 4 ~
0~ 334 poly~alent aliphatic amines or ammonla. As esterification components, there may be used for example ethanol, propanol, butanol, stear~l alcohol or montanol (hydrogenated montan wax), furthermore diols such as ethylene glycol, propanediol-(1,2), butanedlol-(1,3) or diethglenegi~iol, ~nd polyhydric alcohoi~
such a~ trimethylolpropane or pentaerythritol. Saponification components are above all metal ions of the tst, 2nd and 3rd group of the Periodic System, for example ~i+, Na+, K+, ~g2+, Ca2l, A13+, Pb2+ or Cd2~. Sultable su~stances for the amlda-tlon are for example ~m~nes such as ethylamine, stearylamine, ethylene dlamlne, as well as ammonla.
Accordlng to the ln~ention, up to 95% by weight of the bark wax or it~ modlflcation products may be replaced by other natural waxes and/or h~drocarbon waxes or the reflned products or oxldates thereof and the e~terlrlcatlon, saponlflcatlon, partl~l esterl~icatlon, partial saponlflcatlon or amldatlon pro-ducts prepared therefrom ln slmllar manner as the modlflcatlon products of the bark wax; that i~, lt ls posslble and in many c~ses even ad~antageous to use the bark wax or the modlflcatlon products thereof ln adm~xture with these waxes.
By other natural waxes, there are to be understood vege-table or anlmal waxes, ror example sugar cane wax, candelllla wax, ourlcury wax, carnauba wax and dereslnlfied or non-deresi-nl~ied crude montan wax. These natural waxes are sultable as cocomponents, especlally in the ~orm Or thelr reflned products obtàlned for example by treatment wlth aqueous chromosulrurlc acld or by other Xnown Purirlcation processes, which products are known as "partially synthetic waxesn. The refined products 29 are preferably used after ha~ing been converted to esterificatlon, _ 5 _ HO~ 74/F 809 1~4~334 saponification, partial esterification, partial saponification or amidation products known as "partially synthetic ester waxes", especially in the form of the reaction products of montan wax.
Hydrocarbon waxes suitable as cocomponents are natural or synthetic paraffin waxes, microcrystalline waxes and polyole-fines. By polyolefins there are to be understood preferably unhranched ~-olefins having from 16 to 70 carbon atoms in the molecule, for example those obtained by oligomerization 1 10 of ethylene in the presence of organo-aluminum catalysts, furthermore polyolefin waxes obtained by homo- or copolymeri-zation of ethylene and other -olefins, or by thermal, cata-lytic or oxidative degradation of high molecular weight poly-olefins. The hydrocarbon waxes may be oxidized with air and/
, 15 or other oxidation agents, for example chromosulfuric acid.
i Oxidized hydrocarbon waxes are for example also the products ! having an acid number of up to 200, which are obtained ac-cording to U.S. Patent No. 3,756,999 by air oxidation of high molecular weight polyolefins in aqueous dispersion, and which may be after-oxidized with aqueous chromosulfuric acid. The oxidized hydrocarbon waxes are preferably used in the form of their esterification, saponification, partial esterification, partial saponification or amidation products. The natural and hydrocarbon waxes or their derivatives may be used also as mixtures with each other or with themselves in any ratio.
The quantitative ratio of bark wax to cocomponents may be widely varied. Generally, it depends on the character of the q onents used and the kind of the lubrication effect intended, 29 that is, whether a more internal or more external lubricating ~.. . ... . . . . .
.. . : . ~ , .- - . , ~ . - .
" . .
1~4~ 334 effect is desired. Normally, the bark wax amount in the mix-A tures is from 5 to 95 welght %, preferably ~rom 20 to 80 weight and especially from 40 to 80 weight %.
The lubricant combinations are obtained for example by mixing the melts of the cocomponents in the desired ratio.
Another method which has proved to be especially advantageous ; for the preparation of lubricant combinatinns of modification products of bark wax and modification products of natural or hydrocarbon waxes consists in sub~ecting the starting mat~rlals to a common esterlficatlon, saponification~amidation, etc.
In the processing of plastic materials, especially PVC, the lubrlcants in accordance with this invention on the basis of waxes obtained from tree-barks by extraction with allphatic hydrocarbons dlsplay lmproved propertles as compared to the bark waxes hltherto used for this purpose. The waxes in accor-dance with thls invention have a dl~tinct internal lubricating i e~fe¢t, ~o that they are preferably employed ~or the manufac-ture o~ transparent plastlcs articles. Because of the llght I color of the waxes, their use, contrary to the bark wax hither-¦ 20 to known, does not result, or onlg to an lnslgnlflcant ex-¦ tent;in a discoloration of the plastic material, so that lt is now posslble to utilize bark wax whlch in prlnclple ls aval-lable in large amounts for thls purpose-The bark wax u~ed as processlng auxlliary for plastic materlals has a lubricating effect comparable to the most efficient ones of the hitherto known products, namely the wax acid derivatives, and its transparency is even ~ar more super-ior.
29 The lubricating propertles of the bark wax may be wldel~
~ ` ~oa~0334 varied and adapted to any requirements of the industrial prac-tice with the aid of other waxes and/or by conversion to the modification products such as esters, soaps etc. In this manner, for example, any desired gradation between a more inter-nal and a more external lubricating effect can be adjusted.
By using the cadmium or lead salts, a stabilizing effect may be additionally obtained.
The cited possibilities of modifying the lubricating pro-perties of the bark wax by mixing it with other waxes and/or conversion to reaction products may of course be transferred also to bark waxes obtained by different extraction methods, for example with solvent mixtures of aliphatic and aromatic I hydrocarbons. However, because of the different composition and the darker color of these waxes, the high quality of the wax extracted from barks with purely aliphatic hydrocarbons cannot be attained. The cited modifications improve also the properties of the bark waxes necessary for application in other fields, for example in polishing agents, in auxiliaries for the treatment of metals, in hydrophobizing and mold re-lease agents.
The lubricants in accordance with the present invention are added to the thermoplastic material in amounts of from O.I to 5.0%, preferably from 0.1 to 3.0%, relative to the weight of the plastic material, generally simultaneously with further additives usual in plastics processing, such as stabi-lizers, flow improving agents or dyestuffs.
The following examples illustrate the invention.
E X A M P L E 1:
29 A light yellow wax obtained from the bark of a douglas fir ~ 4033~ HOE 74/F 809 (pseudotsuga taxifolia) by extraction with heptane, and having an acid number of 65, a saponification number of 149 and a drop-ping point of 57C is used as lubricant for poly(vinyl chloride.) A mixture of i 5 100.0 parts by weight of suspension poly(vinyl chloride) hav-ing a K value of 65, 0.5 part by weight of bark wax and 1.0 part by weight of an organo-tin compound as stabilizer is processed at 180C on heated rolls. A rolling time of 70 minutes until decomposition is attained without sticking.
From a similar mixture, containing however 1.0 part of the bark wax and 1.5 parts of the stabilizer, rolled as in-dicated above, a plate having a thickness of 2 millimeters is molded. The plate is practically colorless it has a transpa-rency of 90% in a beam of light of a wave length of 741 nano-meters.
For a comparison, the bark wax is replaced by an ester wax on the basis of montan wax. The rolling time in this case is only 44 minutes and the transparency 2%.
E X A M P L E 2: (Comparative Example) A green-brown wax obtained by extraction from the bark of a douglas fir with a heptane/benzene mixture is tested as lubricant as described in Example 1. The rolling time is 69 minutes until decomposition, but the rough sheet starts to stick after 62 minutes already.
The plate manufactured for the transparency test has a transparency of 83%.
_ g _ :
E X A M P ~ E ~:
300 Grams of the bark wax used in Example 1 are saponified by stirring the melt at 110C with 11 grams of calcium hydroxide.
A wax soap is obtained having a residual acid number of 10, a ~aponification number of 120 and a dropping point of 87~C. The wax soap is tested as lubricant in the processing of poly-(~inyl chloride) according to Example 1. A rolling time of 77 minutes until decomposition ~sticking starts after 68 minu-tes) is attained. The manufacture of a test specimen for the transparency test gives a plate having a light color and a transparency of 89~.
E X A M P ~ E 4:
300 Crams of the bark was used in Example 1 in molten state are esterified at 110C with 90 grams of stearyl alcohol ln the presence of eatalytic amounts of sulfuric acld until a resldual acld number of 30 ls attained. The partial ester ob-talned has a saponlficatlon number of 130 and a dropplng point o~ 58&. The ester is used as lubrleant in the proeessing of ;' PVC as deseribed in Example 1. A rolling time of 73 mlnutes until stleking 18 attalned. The test specimen manufactured aeeording to Example 1 has a faintly yellow color, and it~
transparency is 92%.
E X A M P ~ E 5:
100 Grams of the bark wax used in Example 1 are mixed with 100 grams of an ester wax ~n the basis of montan wax hav-lng an acid number of 18 and a saponification number of 138 by stlrring the melts together at 110C. The wax mixture ob-talned is used according to Example 1 as lubricant for the 29 processing of poly(vinyl chloride). A rolling time of 60 minu-. -- 10 --~ '"' . ' ' ' ~ ' . ' ` ' ' ' ': ' ' ' ' ' '' ~ . . : , . ''.-.,, :,:, : -, , - ... ..
OE 74/~ 809 ,_ 104~334 -- tes untll ~ticking is attalned. The te~t specimen ~or measur-ing the transparency ha~ a yellowish color and it~ transparency 18 86~.
E X A M P ~ E 6:
; 120 Cram~ of tne ~arX wax u~ed in Exampl~ 1 ara mixed wlth 80 grams of a poly-ethylene oxldized wlth air and having an acid number of 65, a saponification number oi 110 and a dropping point of 110C (obtained according to the proces~ des-cribed in U.S. Patent No. 3,756,999 by air oxidation ln aque-OUQ dispersion from a high molecular weight pla~tic-like poly-eth~lene). The mixture iQ subsequently ~aponifled by ~tirring the melt with 8 grams of calcium hydroxide until a residual acld number of 5 i8 attained. A wax soap ha~ing a saponifi-cation number of 110 and a dropping point of 105C i~ obtalned.
j 15 U~ed as lubricant ~or the processing o~ poly(vinyl chloride) as ~ndicated in Example 1, a rolli~g timo o~ 75 minutes until stic~klng i_ attained. The test ~pecimen ~or the e~aluation o~ the tran~parency i8 practlcally colorless. The tranQparency 18 9~, . _ 11 -., . i- -.,, .. . . ..... . ., . -. ...... ... ... .. - . . . .
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A plastic composition containing a lubricant, in which the lubricant is a wax obtained by extraction of tree-barks with an aliphatic hydrocarbon and having an acid number of from 20 to 90, saponification number of from 110 to 180 and a melting point of from 45 to 70°C, in an amount of from 0.1 to 5% by weight, relative to the plastic composition.
2. A composition as claimed in claim 1 in which the wax is present in the form of a derivative obtained by oxidation, esterification, saponification, partial esterification, partial saponification or amidation of the wax.
3. A composition as claimed in claim 1 in which the plastic is polyvinyl chloride.
4. A composition as claimed in claim 1, claim 2 or claim 3 in which the wax is present in admixture with another wax.
5. A composition as claimed in claim 1, claim 2 or claim 3 in which the wax is present in admixture with another wax from the group of natural waxes and hydrocarbon waxes and derivatives of these waxes which derivatives are obtained by oxidation, esterification, saponification, partial esterifica-tion, partial saponification or amidation.
6. A composition as claimed in claim 1, claim 2 or claim 3 in which the wax is present in admixture with another wax selected from the group of nature and synthetic parafin waxes, microcrystalline waxes and polyolefines from the group of unbranched .alpha.-olefins having from 16 to 70 carbon atoms in the molecule.
7. A composition as claimed in claim 1, claim 2 or claim 3 in which the lubricant is present in an amount of from 0.1 to 3.0%.
8. A process for the preparation of a plastic composition containing a lubricant in which a plastic composition is mixed with 0.1 to 5% by weight of a lubricant, relative to the plastic composition, the lubricant being a wax obtained by extraction of tree-barks with an aliphatic hydrocarbon and having an acid number of from 20 to 90, a saponification number of from 110 to 180 and a melting point of from 45 to 70°C.
9. A process as claimed in claim 8 in which the lubricant is used in the form of a derivative obtained by oxidation, esteri-fication, saponification, partial esterification, partial sap-onification or amidation of the wax.
10. A process as claimed in claim 8 in which the plastic is polyvinyl chloride.
11. A process as claimed in claim 8, claim 9 or claim 10 in which the lubricant additionally comprises another wax.
12. A process as claimed in claim 8, claim 9 or claim 10 in which the lubricant additionally comprises another wax from the group of natural waxes and hydrocarbon waxes and derivatives of these waxes, which derivatives are obtained by oxidation, esterification, saponification, partial esterifi-cation, partial saponification or amidation.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742452013 DE2452013C2 (en) | 1974-11-02 | Use of waxes as a lubricant for plastics processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040334A true CA1040334A (en) | 1978-10-10 |
Family
ID=5929838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,819A Expired CA1040334A (en) | 1974-11-02 | 1975-10-31 | Lubricants for the processing of plastic materials |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE835198A (en) |
| CA (1) | CA1040334A (en) |
| FR (1) | FR2289554A1 (en) |
| GB (1) | GB1487503A (en) |
| IT (1) | IT1044305B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2727329C2 (en) * | 1977-06-16 | 1984-03-01 | Akzo Gmbh, 5600 Wuppertal | Olefin-maleic acid copolymer ester |
| CN116948328B (en) * | 2023-09-20 | 2023-12-08 | 山东宏福化学有限公司 | PVC lubricant and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662893A (en) * | 1950-03-28 | 1953-12-15 | Oregon State | Extraction of valuable products from bark |
| FR1302635A (en) * | 1961-07-21 | 1962-08-31 | Radiologie Cie Gle | Compression system for X-ray examination device |
| DE1245201B (en) * | 1965-05-08 | 1967-07-20 | Gisela Vennmann Geb Berns | Milking machine with a piston pump generating negative pressure |
| US3789058A (en) * | 1972-03-08 | 1974-01-29 | F Trocino | Method of extracting wax from bark |
-
1975
- 1975-10-31 IT IT2889575A patent/IT1044305B/en active
- 1975-10-31 GB GB4529175A patent/GB1487503A/en not_active Expired
- 1975-10-31 CA CA238,819A patent/CA1040334A/en not_active Expired
- 1975-11-03 FR FR7533512A patent/FR2289554A1/en active Granted
- 1975-11-03 BE BE161538A patent/BE835198A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE835198A (en) | 1976-05-03 |
| FR2289554B1 (en) | 1979-07-13 |
| FR2289554A1 (en) | 1976-05-28 |
| IT1044305B (en) | 1980-03-20 |
| DE2452013A1 (en) | 1975-07-03 |
| DE2452013B1 (en) | 1975-07-03 |
| GB1487503A (en) | 1977-10-05 |
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