CA2074821A1 - Basic calcium aluminum hydroxide dicarboxylates, a process for their production and their use - Google Patents
Basic calcium aluminum hydroxide dicarboxylates, a process for their production and their useInfo
- Publication number
- CA2074821A1 CA2074821A1 CA002074821A CA2074821A CA2074821A1 CA 2074821 A1 CA2074821 A1 CA 2074821A1 CA 002074821 A CA002074821 A CA 002074821A CA 2074821 A CA2074821 A CA 2074821A CA 2074821 A1 CA2074821 A1 CA 2074821A1
- Authority
- CA
- Canada
- Prior art keywords
- dicarboxylates
- aluminum hydroxide
- calcium
- production
- basic calcium
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
- C07C63/28—Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/08—Malonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/10—Succinic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/13—Dicarboxylic acids
- C07C57/145—Maleic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/13—Dicarboxylic acids
- C07C57/15—Fumaric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/16—1,2 - Benzenedicarboxylic acid
- C07C63/20—Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/24—1,3 - Benzenedicarboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Abstract
Abstract The invention describes basic calcium aluminum hydro-xide dicarboxylates of the general formula CaxAl2(OH)2(x+2)A ? m H2O
wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dicarboxylic acid anion or combinations thereof and a process for their production.
The compounds according to the invention are especially suited as stabilizers for halogen-containing, thermo-plastic resins, in particular PVC.
wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dicarboxylic acid anion or combinations thereof and a process for their production.
The compounds according to the invention are especially suited as stabilizers for halogen-containing, thermo-plastic resins, in particular PVC.
Description
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Specification The invention relates to basic calcium aluminum hydro-xide dicarboxylates, a process for their production and their use as stabilizers for halogen-containing, thermoplastic resins, in part:icular polyvinyl chloride.
Thermoplastic, halogen-containing rasins, in particular PVC, are instable to the influence of heat and light. A
thermal decomposition of the resin already occurs in the processing of e.g. unstablized PVC. This is mani-fested in a discolouring of the shaped article and in the deterioration of the mechanical properties. To exclude this disadvantage it is necessary to incor-porate heat stabilizers into the resin composition. For this purpose, organic and/or inorganic compounds of the metals lead, barium, cadmium, calcium, tin and zinc are customarily added alone or in combinations. In addition to this, other costabilizers such as epoxides, organic sulphur compounds, polyols and phosphites are still added.
Basic lead compounds are preferably used for stabiliz-ing PVC articles such as tubes, plates, profiles and cable insulations. The most frequently used basic lead compounds are of the sulphate, phosphite or stearate type.
DE-PS 12 19 223 and DE-OS 24 l9 379 teach that PVC
cable insulations can preferably be stabilized with 2-basic lead phthalate, since this compound imparts the cable excellent electric properties.
It is mentioned in EP-A- 0 313 113 that 4-basic lead fumarate is the most effective basic lead compound for ,.
~,. ~:. , 2~17~821 stabilizing plasticized, halogen-containing vinyl polymer compositions. According to EP-A-o 319 086 5-basic lead ~umarate~ imparts shaped PVC articles a higher stability and a batter degree of whiteness than other known lead stabilizers.
The organic and/or inorganic ~ompounds of the heavy metals lead, barium and cadmium are rated as toxic. ~or this reason, attempts have b~en made for a long time to replace them by non-toxic compounds. The s~abilizers on the basis of combinations of calcium and zinc carboxy-lates, which are considered to be non-toxic, are insufficient in their effectiveness in most fields of application. Their disadvantages are manifested in a non-sufficient long-term stability and/or an unsatis-factory initial colour and colour retention. The combination of these metallic soaps with effective costabilizers which improve the initial colour and long-term tability is therefore imperative. It is described in FR-A 2 403 362 to stabilize plasticized PVC for cable insulations with a mixture of calcium zinc fatty acids, sorbite and a B-diketone. EP-A- 0256 872 describes the use of hydrotalcite and a B-diketone for stabilizing PVC resins. Alkali alumino silicates in connection with other costabilizers were also suggested to be used in PVC (DE-A- 31 13 442~.
However, all non-toxic stabilizing systems suggested so far have disadvantayes as compared with hPavy metal containing stabilizers. Mostly, they do not have the necessary long-term stability. A good initial colour and a sufficient colour retention can only be achiaved by the use of large amounts of expensive "colour improvers". The metal-containing costabilizers hydro-talcite and zeolite are disadvantageous inasmuch as .
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207~82~ `
they split off volatile compounds at the processing temperatures necessary for the processing of e.g. PVC, which leads to bubble formation in the shaped article.
Shaped PVC articles stabilized e.g. with polyol and/or zeolite take up water, which leads to considPrable problems in the further processing.
The invention is based on the object of providing new compounds and a process for their production, which are especially suited as a stabilizer for halogen-contain-ing polymers without having the aforementioned disad-vantages of the known stabilizers, and which are in particular regarded as ton-toxic.
This object is accomplished by the invention, on the one hand, by the provision of basic calcium aluminum hydroxide dicarboxylates of th~ general formula CaxAl2(oH)2~x+2)A m H20 wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dicarboxyl1c acid anion or combinations thereof.
X means preferably 3 - 6 and m means preferably 2 - 4 in the aforementioned formula.
acid The dicarboxylic~anions indicated with A are e.g.
derived from malonic acid, succinic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terPphthalic acid and pyridine dicarboxylic acids. The fumarate and phthalate anion form part of the preferred dicarboxylic acid anions.
: ~ . : . ; . :; .
, :' ;';' . , ' ;.
. '~ ' ., ' ' ' ' . . .
' . ~ . ; ,~ . ' 207~821 Examinations by means of X-ray diffraction showed that the dicarboxylates according to the invention do not fall under the hydrotalcite type regarding their crystal structure.
It became surprisingly apparent that the calcium aluminum hydroxide dicarboxylal:es according to the in-vention impart comparable heat: stabilities like basic lead compounds to halogen-containing, thermoplastic resins and shaped articles produced there~rom. Th~
initial colours and the colour retention of e.g~ shaped unplasticized PVC articles which are stabilized with one of the new compounds according to the invention are equivalent to the same shaped articles which contain known non-toxic stabilizer systems.
The object on which the invention is based is, on the other hand, solved by a process Por the production of the calcium aluminum hydroxide dicarboxylates according to the invention, which is characterized in that mixtures of calcium hydroxide and/or calcium oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and/or calcium oxide and sodium aluminate ars reacted with the corresponding dicarboxylic acid in amounts corresponding to the production of the desired compounds in an aqueous medium and the reaction product is separated and recovered in a manner known per se.
The reaction product directly obtained from the reac-tion described above can be separated from the aqueous reaction medium according to known processes, prefer-ably by means of filtration. The processing of the separated reaction product is also carried out in a manner known per se, e.y. by washing the filter cake with water and drying the washed residue at tampera-tures of e.g. 60 - 130C, preferably at 90 - 1~0C.
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Both a finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium alumi-nate can be used for the reactio~. Calcium can be used in the form of finely divided calcium oxide or calcium hydroxide or mixtures thereof.
The reaction temperatures are preferably between abou~
25 and 100C, ~urthermore preferably between about 40 and 85C. Catalysts or accelerators are not necessary, but can possibly be also used. The crystal water can be removed wholly or partly by thermal treatment in the compounds according to the invention.
If they are used as stabilizers the dried calcium aluminum hydroxide dicarboxylates according to the invention do not split off any water at the processing temperatures of 160 - 200C, which are e.g. customary for unplasticized PVC so that no disturbing bubble formation occurs in the shaped articles.
To improve their dispersibility in halogen-containing, thermoplastic resins the compounds according to the invention can be coated in known fashion with surface-active agents.
According to the invention halogen-containing, thermo-plastic resins can be stabilized with the calcium aluminum hydroxide dicarboxylates according to the invention. Polyvinyl chlorides, homopolymers and copolymers thereof and their mixtures with other polymers such as ABS (copolymer of acrylonitrile butadiene / styrene), CPVC (post-chlorinated PVC), acrylates and the like, which are produced in ~no~n fashion, are especially suited for this.
.
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In addition to the compounds according to the inven-tion, further additives can of course be incorporated into the resin. Examples of such additives are: organo-tin compounds, organic phosphites, epoxy compounds, amino compounds, polyhydric alcohols, metallic soaps of C8 ~ C22 fatty acids with the metals Ca, Zn, Mg or Al, antioxidants, W absorbers, carbonyl compoundsl anti-static agents, lubricants, plasticizers, pigments and fillers.
The invention is explained in greater detail by means of the following examples.
A) Production of the basic calcium aluminum hydroxide dicarboxylates according to the invention, Example 1 An aqueous suspension (4.5 l) of 296 g of calcium hydroxide (4 mol) and 164 g of sodium aluminate (2 mol) is heated to 50C. Subsequently 232 g of fumaric acid (2 mol) is added under stirring in the form of a 10%
aqueous solution heated to 85C at constant feed rate in the course of 30 minutes. Thereupon the suspension is heated to 70C and stirring is carried out at this temperature for 2 hours. 10 minutes before the end of the reaction time 4 g of sodium stearate are added for coating. The suspension obtained in this fashion is filtered off and washed with 1.8 l of water~ The filter cake formed in this fashion is dried at 125C in a drying cupboard for 4 hours.
The analysis values of the product are indicated below.
. .
- . , . :, . ~, . . . . .. .
2 ~ 8 ~ 1 Mol ratio Found value Calculated value Ca 4.1 4.0 Al 1.8 2.0 C 4.3 4.0 Example 2 An aqueous suspension (5.0 1) of 222 g of calcium hydroxide (3 mol), 80 g of sodium hydroxide (2 mol) and 156 g of ac~ive aluminum hydroxide (2 mol) is heated to 70C. Subsequently 332 g of phthalic acid (2 mol) in the form of an 8% aqueous solution (temperature 85C~
are added under stirring at con tant feed rate in the course of 30 minutes. Thereupon the suspension is heated to 80C and stirring is carried out at this temperature for 2 hours. 10 minutes before the end of the reaction time 4 g of sodium stearate are ~dded for coating. The suspension obtained in this fashion is filtered off, washed with 1.2 1 of water and the filter cake is dried at 130C in a drying cupboard for 4 hours. The analysis values of the product produced in this fashion are indicated below.
Mol ratio Found valueCalculated value Ca 3,05 3 0 Al 1.95 2.0 C 7.2 8.0 B) Use of the compounds according to the invention as stabilizers 2~7'~2~
The heat stability and the initial color of shaped PVC
bodies to which the compounds according to the inven-tion were been added are evaluated in the following examples.
The mixtures used in ~he following examples are homo-genized and plasticized at lBOC for 5 minutes on a laboratory rolling mill to evaluate the heat stability.
Square sample sheets of an edge length of 15 mm are cut out from the sheet produced in this fashion, which is about 1 mm thick. The sample sheets are tempered in a heating cupboard at 190C. one sheet each is withdrawn at an interval of 10 minutes and attached to a test card. This process is repeated until the sample sheets have a black discolouring.
, ; . , ................. : ,:
~: :
- 2~7~82~.
Example 3 Parts ~ ~ C
PVC (K68) 100 100 100 Impact stren~th additive 10 10 10 Chalk 5 5 5 Tio2 4 4 Distearyl phthalate 0.6 0.6 0.6 Bisphenol A 0.2 0.2 0.2 Lead stearate 1.0 - -Dibasic lead phthalate 2.0 - -Calcium stearate 0.5 1.0 1.0 Zinc stearate - 0.5 0.5 Ca4Al2toH)l2 C4~24 Ca3Al2(oH)lo C8H44 Dibenzoyl methane - O~1 0.1 The aforementioned compositions o~ A to C were tested according to the indicated method. The results axe summarized in table I.
.
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.
- ~
~07~82 1 -- 12 -- .
Table I: Results of the evaluation of thermal stability Time ~min . ) compo~ition 0 10 20 30 40 60 80 _100_ 120 140 lG0 B l 11 1 2 2 2 3 4 4 6 c 1 l1 2 2 2 4 4 4 4 6 1 = white 2 = silightly yellow 3 - slightly grey 4 - yellow 5 = grey 6 = brown . ~ , , : .
`
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Example 4 Parts by weiqht D E F
_ _ Chalk 60 60 60 Tio2 2 2 2 Dioctyl phthalate 50 50 50 Bisphenol A 0.2 0.2 0.2 Dibasic lead phthalate 2.0 - -Lead stearate 1.0 - -Calcium stearate 0.5 1.0 1.O
Zinc stearate - 0.5 0.5 Ca4A12(OH)l2 C4H24 Ca3Al2(o~)lo C8H44 The aforementioned compositions of D to F were tested according to the indicated method and the thermal stability was evaluated. The results are summarized in table II.
. : . : .
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2~7~2~
Table II
Time ~min . ) Com~osition0 _1020 _ 40 60 80 120 160 180 200 D lll 1 3 3 3 3 3 5 E 11l 1 2 2 3 3 4 6 F l11 1 1 2 2 4 4 6 1 = white 2 - slishtly yellow 3 i slightly grey 4 = yellow 5 = grey 6 - brown .. , ; . . . .
,, . ,, :
, , ' ", " ' '
Specification The invention relates to basic calcium aluminum hydro-xide dicarboxylates, a process for their production and their use as stabilizers for halogen-containing, thermoplastic resins, in part:icular polyvinyl chloride.
Thermoplastic, halogen-containing rasins, in particular PVC, are instable to the influence of heat and light. A
thermal decomposition of the resin already occurs in the processing of e.g. unstablized PVC. This is mani-fested in a discolouring of the shaped article and in the deterioration of the mechanical properties. To exclude this disadvantage it is necessary to incor-porate heat stabilizers into the resin composition. For this purpose, organic and/or inorganic compounds of the metals lead, barium, cadmium, calcium, tin and zinc are customarily added alone or in combinations. In addition to this, other costabilizers such as epoxides, organic sulphur compounds, polyols and phosphites are still added.
Basic lead compounds are preferably used for stabiliz-ing PVC articles such as tubes, plates, profiles and cable insulations. The most frequently used basic lead compounds are of the sulphate, phosphite or stearate type.
DE-PS 12 19 223 and DE-OS 24 l9 379 teach that PVC
cable insulations can preferably be stabilized with 2-basic lead phthalate, since this compound imparts the cable excellent electric properties.
It is mentioned in EP-A- 0 313 113 that 4-basic lead fumarate is the most effective basic lead compound for ,.
~,. ~:. , 2~17~821 stabilizing plasticized, halogen-containing vinyl polymer compositions. According to EP-A-o 319 086 5-basic lead ~umarate~ imparts shaped PVC articles a higher stability and a batter degree of whiteness than other known lead stabilizers.
The organic and/or inorganic ~ompounds of the heavy metals lead, barium and cadmium are rated as toxic. ~or this reason, attempts have b~en made for a long time to replace them by non-toxic compounds. The s~abilizers on the basis of combinations of calcium and zinc carboxy-lates, which are considered to be non-toxic, are insufficient in their effectiveness in most fields of application. Their disadvantages are manifested in a non-sufficient long-term stability and/or an unsatis-factory initial colour and colour retention. The combination of these metallic soaps with effective costabilizers which improve the initial colour and long-term tability is therefore imperative. It is described in FR-A 2 403 362 to stabilize plasticized PVC for cable insulations with a mixture of calcium zinc fatty acids, sorbite and a B-diketone. EP-A- 0256 872 describes the use of hydrotalcite and a B-diketone for stabilizing PVC resins. Alkali alumino silicates in connection with other costabilizers were also suggested to be used in PVC (DE-A- 31 13 442~.
However, all non-toxic stabilizing systems suggested so far have disadvantayes as compared with hPavy metal containing stabilizers. Mostly, they do not have the necessary long-term stability. A good initial colour and a sufficient colour retention can only be achiaved by the use of large amounts of expensive "colour improvers". The metal-containing costabilizers hydro-talcite and zeolite are disadvantageous inasmuch as .
,. . : ~. ~; . :
207~82~ `
they split off volatile compounds at the processing temperatures necessary for the processing of e.g. PVC, which leads to bubble formation in the shaped article.
Shaped PVC articles stabilized e.g. with polyol and/or zeolite take up water, which leads to considPrable problems in the further processing.
The invention is based on the object of providing new compounds and a process for their production, which are especially suited as a stabilizer for halogen-contain-ing polymers without having the aforementioned disad-vantages of the known stabilizers, and which are in particular regarded as ton-toxic.
This object is accomplished by the invention, on the one hand, by the provision of basic calcium aluminum hydroxide dicarboxylates of th~ general formula CaxAl2(oH)2~x+2)A m H20 wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dicarboxyl1c acid anion or combinations thereof.
X means preferably 3 - 6 and m means preferably 2 - 4 in the aforementioned formula.
acid The dicarboxylic~anions indicated with A are e.g.
derived from malonic acid, succinic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terPphthalic acid and pyridine dicarboxylic acids. The fumarate and phthalate anion form part of the preferred dicarboxylic acid anions.
: ~ . : . ; . :; .
, :' ;';' . , ' ;.
. '~ ' ., ' ' ' ' . . .
' . ~ . ; ,~ . ' 207~821 Examinations by means of X-ray diffraction showed that the dicarboxylates according to the invention do not fall under the hydrotalcite type regarding their crystal structure.
It became surprisingly apparent that the calcium aluminum hydroxide dicarboxylal:es according to the in-vention impart comparable heat: stabilities like basic lead compounds to halogen-containing, thermoplastic resins and shaped articles produced there~rom. Th~
initial colours and the colour retention of e.g~ shaped unplasticized PVC articles which are stabilized with one of the new compounds according to the invention are equivalent to the same shaped articles which contain known non-toxic stabilizer systems.
The object on which the invention is based is, on the other hand, solved by a process Por the production of the calcium aluminum hydroxide dicarboxylates according to the invention, which is characterized in that mixtures of calcium hydroxide and/or calcium oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and/or calcium oxide and sodium aluminate ars reacted with the corresponding dicarboxylic acid in amounts corresponding to the production of the desired compounds in an aqueous medium and the reaction product is separated and recovered in a manner known per se.
The reaction product directly obtained from the reac-tion described above can be separated from the aqueous reaction medium according to known processes, prefer-ably by means of filtration. The processing of the separated reaction product is also carried out in a manner known per se, e.y. by washing the filter cake with water and drying the washed residue at tampera-tures of e.g. 60 - 130C, preferably at 90 - 1~0C.
- :~ - :- . , . ;
.:
. ~ :
~: : ,.;
:
, 2 ~
Both a finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium alumi-nate can be used for the reactio~. Calcium can be used in the form of finely divided calcium oxide or calcium hydroxide or mixtures thereof.
The reaction temperatures are preferably between abou~
25 and 100C, ~urthermore preferably between about 40 and 85C. Catalysts or accelerators are not necessary, but can possibly be also used. The crystal water can be removed wholly or partly by thermal treatment in the compounds according to the invention.
If they are used as stabilizers the dried calcium aluminum hydroxide dicarboxylates according to the invention do not split off any water at the processing temperatures of 160 - 200C, which are e.g. customary for unplasticized PVC so that no disturbing bubble formation occurs in the shaped articles.
To improve their dispersibility in halogen-containing, thermoplastic resins the compounds according to the invention can be coated in known fashion with surface-active agents.
According to the invention halogen-containing, thermo-plastic resins can be stabilized with the calcium aluminum hydroxide dicarboxylates according to the invention. Polyvinyl chlorides, homopolymers and copolymers thereof and their mixtures with other polymers such as ABS (copolymer of acrylonitrile butadiene / styrene), CPVC (post-chlorinated PVC), acrylates and the like, which are produced in ~no~n fashion, are especially suited for this.
.
~, , , ~ .
. .
2~7~32~
In addition to the compounds according to the inven-tion, further additives can of course be incorporated into the resin. Examples of such additives are: organo-tin compounds, organic phosphites, epoxy compounds, amino compounds, polyhydric alcohols, metallic soaps of C8 ~ C22 fatty acids with the metals Ca, Zn, Mg or Al, antioxidants, W absorbers, carbonyl compoundsl anti-static agents, lubricants, plasticizers, pigments and fillers.
The invention is explained in greater detail by means of the following examples.
A) Production of the basic calcium aluminum hydroxide dicarboxylates according to the invention, Example 1 An aqueous suspension (4.5 l) of 296 g of calcium hydroxide (4 mol) and 164 g of sodium aluminate (2 mol) is heated to 50C. Subsequently 232 g of fumaric acid (2 mol) is added under stirring in the form of a 10%
aqueous solution heated to 85C at constant feed rate in the course of 30 minutes. Thereupon the suspension is heated to 70C and stirring is carried out at this temperature for 2 hours. 10 minutes before the end of the reaction time 4 g of sodium stearate are added for coating. The suspension obtained in this fashion is filtered off and washed with 1.8 l of water~ The filter cake formed in this fashion is dried at 125C in a drying cupboard for 4 hours.
The analysis values of the product are indicated below.
. .
- . , . :, . ~, . . . . .. .
2 ~ 8 ~ 1 Mol ratio Found value Calculated value Ca 4.1 4.0 Al 1.8 2.0 C 4.3 4.0 Example 2 An aqueous suspension (5.0 1) of 222 g of calcium hydroxide (3 mol), 80 g of sodium hydroxide (2 mol) and 156 g of ac~ive aluminum hydroxide (2 mol) is heated to 70C. Subsequently 332 g of phthalic acid (2 mol) in the form of an 8% aqueous solution (temperature 85C~
are added under stirring at con tant feed rate in the course of 30 minutes. Thereupon the suspension is heated to 80C and stirring is carried out at this temperature for 2 hours. 10 minutes before the end of the reaction time 4 g of sodium stearate are ~dded for coating. The suspension obtained in this fashion is filtered off, washed with 1.2 1 of water and the filter cake is dried at 130C in a drying cupboard for 4 hours. The analysis values of the product produced in this fashion are indicated below.
Mol ratio Found valueCalculated value Ca 3,05 3 0 Al 1.95 2.0 C 7.2 8.0 B) Use of the compounds according to the invention as stabilizers 2~7'~2~
The heat stability and the initial color of shaped PVC
bodies to which the compounds according to the inven-tion were been added are evaluated in the following examples.
The mixtures used in ~he following examples are homo-genized and plasticized at lBOC for 5 minutes on a laboratory rolling mill to evaluate the heat stability.
Square sample sheets of an edge length of 15 mm are cut out from the sheet produced in this fashion, which is about 1 mm thick. The sample sheets are tempered in a heating cupboard at 190C. one sheet each is withdrawn at an interval of 10 minutes and attached to a test card. This process is repeated until the sample sheets have a black discolouring.
, ; . , ................. : ,:
~: :
- 2~7~82~.
Example 3 Parts ~ ~ C
PVC (K68) 100 100 100 Impact stren~th additive 10 10 10 Chalk 5 5 5 Tio2 4 4 Distearyl phthalate 0.6 0.6 0.6 Bisphenol A 0.2 0.2 0.2 Lead stearate 1.0 - -Dibasic lead phthalate 2.0 - -Calcium stearate 0.5 1.0 1.0 Zinc stearate - 0.5 0.5 Ca4Al2toH)l2 C4~24 Ca3Al2(oH)lo C8H44 Dibenzoyl methane - O~1 0.1 The aforementioned compositions o~ A to C were tested according to the indicated method. The results axe summarized in table I.
.
- ~ . . : .
.
- ~
~07~82 1 -- 12 -- .
Table I: Results of the evaluation of thermal stability Time ~min . ) compo~ition 0 10 20 30 40 60 80 _100_ 120 140 lG0 B l 11 1 2 2 2 3 4 4 6 c 1 l1 2 2 2 4 4 4 4 6 1 = white 2 = silightly yellow 3 - slightly grey 4 - yellow 5 = grey 6 = brown . ~ , , : .
`
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2~7~
Example 4 Parts by weiqht D E F
_ _ Chalk 60 60 60 Tio2 2 2 2 Dioctyl phthalate 50 50 50 Bisphenol A 0.2 0.2 0.2 Dibasic lead phthalate 2.0 - -Lead stearate 1.0 - -Calcium stearate 0.5 1.0 1.O
Zinc stearate - 0.5 0.5 Ca4A12(OH)l2 C4H24 Ca3Al2(o~)lo C8H44 The aforementioned compositions of D to F were tested according to the indicated method and the thermal stability was evaluated. The results are summarized in table II.
. : . : .
:
2~7~2~
Table II
Time ~min . ) Com~osition0 _1020 _ 40 60 80 120 160 180 200 D lll 1 3 3 3 3 3 5 E 11l 1 2 2 3 3 4 6 F l11 1 1 2 2 4 4 6 1 = white 2 - slishtly yellow 3 i slightly grey 4 = yellow 5 = grey 6 - brown .. , ; . . . .
,, . ,, :
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Claims (8)
Basic Calcium Aluminum Hydroxide Dicarboxylates, a Process for their Production and their Use Claims
1) Basic calcium aluminum hydroxide dicarboxylates of the general formula CaxAl2(OH)2(x+2)A ? m H2O
wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dixarboxylic acid anion or combinations thereof.
wherein x means 2 - 8, m means 0 - 12 and A means an aliphatic, aromatic or heteroaromatic dixarboxylic acid anion or combinations thereof.
2) Dicarboxylates according to claim 1 wherein x means 3 - 6.
3) Dicarboxylates according to claim 1 and/or 2, wherein m means 2 - 4.
4) Dicarboxylates according to at least any of claims 1 to 3, wherein A is the fumarate anion.
5) Dicarboxylates according to at least any of claims 1 to 3, wherein A is the phthalate anion.
6) A process for the production of the basic calcium aluminum hydroxide dicarboxylates according to claims 1 to 5, characterized in that mixtures of calcium hydro-xide and/or calcium oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and/or calcium oxide and sodium aluminate are reacted with the corres-ponding dicarboxylic acid in amounts corresponding to the production of the desired compounds in an aqueous medium and the reaction product is separated and recovered in a manner known per se.
7) A process according to claim 6, wherein the reaction is carried out at a temperature between about 25 and 100°C.
8) Use of the basic calcium aluminum hydroxide dicarbo-xylates according to claims 1 to 5 as stabilizers for halogen-containing thermoplastic resins, in particular polyvinyl chloride.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4002988.3 | 1990-02-01 | ||
DE4002988A DE4002988A1 (en) | 1990-02-01 | 1990-02-01 | Basic calcium aluminium hydroxide di:carboxylate(s) - useful as heat stabilisers for halogen-contg. thermoplastics, esp. PVC |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2074821A1 true CA2074821A1 (en) | 1991-08-02 |
Family
ID=6399224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002074821A Abandoned CA2074821A1 (en) | 1990-02-01 | 1991-01-17 | Basic calcium aluminum hydroxide dicarboxylates, a process for their production and their use |
Country Status (13)
Country | Link |
---|---|
US (1) | US5241094A (en) |
EP (1) | EP0513087A1 (en) |
JP (1) | JPH05503931A (en) |
KR (1) | KR927003502A (en) |
CN (1) | CN1054417A (en) |
AU (1) | AU7072791A (en) |
CA (1) | CA2074821A1 (en) |
CS (1) | CS20091A2 (en) |
DE (1) | DE4002988A1 (en) |
IE (1) | IE910329A1 (en) |
PT (1) | PT96618A (en) |
WO (1) | WO1991011421A1 (en) |
ZA (1) | ZA91458B (en) |
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DE4106404C2 (en) * | 1991-02-28 | 1995-05-18 | Baerlocher Gmbh | Calcium aluminum hydroxide dicarboxylates, process for their preparation and their use |
EP0572151A3 (en) * | 1992-05-28 | 1995-01-18 | Avx Corp | Varistors with sputtered terminations and a method of applying sputtered teminations to varistors and the like. |
US5565838A (en) * | 1992-05-28 | 1996-10-15 | Avx Corporation | Varistors with sputtered terminations |
DE4238567A1 (en) * | 1992-11-16 | 1994-05-19 | Henkel Kgaa | Stabilizer mixtures for polymers with grenades |
DE4325237A1 (en) * | 1993-07-28 | 1995-02-02 | Basf Ag | Process for the preparation of alkoxylation products in the presence of mixed hydroxides modified with additives |
FR2722792B1 (en) * | 1994-07-21 | 1996-09-06 | Ceca Sa | COMPOSITIONS OF THE MIXED HYDROXIDE TYPE OF ALUMINUM AND ALKALINE EARTH AS ANTICHLORINE AND ANTI-ACID AGENTS FOR THE STABILIZATION OF THERMOPLASTIC RESINS |
DE19627258C2 (en) * | 1996-07-08 | 2001-04-12 | Chemson Polymer Additive | Process for producing a fusible stabilizer combination |
DE10118179A1 (en) * | 2001-04-11 | 2002-10-24 | Baerlocher Gmbh | Stabilizer combination, useful for halogen containing polymers comprises at least one aminoalcohol and a halogen containing salt of an oxy-acid and/or at least one aminocrotonate compound. |
DE10124734A1 (en) * | 2001-05-21 | 2002-12-05 | Baerlocher Gmbh | Finely divided stabilizer composition for halogen-containing polymers |
US6887926B1 (en) | 2001-11-16 | 2005-05-03 | Oatey Co. | Bonding compositions for chlorinated polymers and methods of using the same |
DE10160662A1 (en) * | 2001-12-11 | 2003-06-18 | Baerlocher Gmbh | Stabilizer composition, useful for foamed material and polymer composition useful for production of hard or (especially) soft PVC, contains an organic onium perchlorate |
US20050192401A1 (en) * | 2002-08-15 | 2005-09-01 | Baerlocher Gmbh | Aid and method for processing thermoplastic polymer compositions |
DE10255155B4 (en) | 2002-11-26 | 2006-02-23 | Baerlocher Gmbh | Stabilizing composition for halogen-containing polymers, process for their preparation and their use |
DE10352762A1 (en) * | 2003-11-12 | 2005-06-16 | Baerlocher Gmbh | Stabilizer composition for halogen-containing thermoplastic resin compositions |
DE10359318A1 (en) * | 2003-12-17 | 2005-07-14 | Baerlocher Gmbh | Stabilizer composition for halogenated polymers |
DE102004019947A1 (en) * | 2004-04-23 | 2005-11-17 | Baerlocher Gmbh | Stabilizer composition for halogen-containing thermoplastic resin compositions having improved shelf life |
DE102004028821A1 (en) * | 2004-06-15 | 2006-01-12 | Baerlocher Gmbh | Stabilizer composition for colored halogen-containing thermoplastic resin compositions |
DE102004060928A1 (en) * | 2004-12-17 | 2006-06-29 | Baerlocher Gmbh | Antistatic polymer composition, its preparation and use |
US10300167B2 (en) | 2006-03-24 | 2019-05-28 | Cabertech, Inc. | Functionalized calcium phosphate artificial bone and joint compositions and methods of use and manufacture |
US20070224678A1 (en) * | 2006-03-24 | 2007-09-27 | Mcgowan Kenneth A | Functionalized artificial bone and joint compositions and methods of use and manufacture |
DE102008053629B4 (en) | 2008-10-29 | 2012-09-06 | Baerlocher Gmbh | Glycerine ether-containing stabilizer composition for halogen-containing polymers, and their use |
WO2011054537A1 (en) | 2009-11-06 | 2011-05-12 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | Sodium fumarate-sodium malonate |
DE102009052206A1 (en) | 2009-11-06 | 2011-05-12 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | Low zinc stabilizer composition for window profiles |
DE102010020263A1 (en) | 2010-05-11 | 2011-11-17 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | Tin-free stabilizer composition |
DE102010034512A1 (en) | 2010-08-16 | 2012-02-16 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | Stabilizer combination for PVC |
EP2886594A1 (en) | 2013-12-18 | 2015-06-24 | Baerlocher GmbH | Liquid zinc salt preparation as stabilizer for halogenated polymers |
EP3712204A1 (en) | 2019-03-18 | 2020-09-23 | Baerlocher GmbH | Metal hydroxycarbonates for pipes |
EP4067422A1 (en) | 2021-03-22 | 2022-10-05 | Baerlocher GmbH | Method for treating halogenated polymers |
CN114181477A (en) * | 2021-12-22 | 2022-03-15 | 成都绮萝科技有限公司 | Safe and environment-friendly PVC stabilizer and preparation method thereof |
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JPS5930737B2 (en) * | 1975-10-18 | 1984-07-28 | 三井化学株式会社 | polyolefin composition |
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JPS554330A (en) * | 1978-06-23 | 1980-01-12 | Takeda Chem Ind Ltd | Maleic anhydride - hydrotalcite complex compound |
US4294745A (en) * | 1979-01-16 | 1981-10-13 | Ciba-Geigy Corporation | Curable mixture for producing reinforced elastomeric plastics based on epoxide resin |
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JPS60104141A (en) * | 1983-11-12 | 1985-06-08 | Kyowa Chem Ind Co Ltd | Agricultural film |
CA1290137C (en) * | 1984-06-11 | 1991-10-08 | John L. Burba, Iii | Intercalations of crystalline lithium aluminates |
JPS61174270A (en) * | 1985-01-29 | 1986-08-05 | Kyowa Chem Ind Co Ltd | Rust-inhibiting or discoloration-resistant synthetic resin composition and agent |
JPH0647659B2 (en) * | 1985-09-24 | 1994-06-22 | 協和化学工業株式会社 | Anticorrosion paint composition |
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DE3869568D1 (en) * | 1987-12-01 | 1992-04-30 | Akzo Nv | PENTABASIC LEAD FUMARATE. |
JP2551802B2 (en) * | 1987-12-29 | 1996-11-06 | 日本合成化学工業株式会社 | Halogen-containing thermoplastic resin composition |
JP2748540B2 (en) * | 1989-04-28 | 1998-05-06 | 大日本インキ化学工業株式会社 | Polyphenylene sulfide resin composition |
-
1990
- 1990-02-01 DE DE4002988A patent/DE4002988A1/en active Granted
-
1991
- 1991-01-07 US US07/916,106 patent/US5241094A/en not_active Expired - Fee Related
- 1991-01-17 JP JP3503062A patent/JPH05503931A/en active Pending
- 1991-01-17 WO PCT/EP1991/000077 patent/WO1991011421A1/en not_active Application Discontinuation
- 1991-01-17 EP EP91903195A patent/EP0513087A1/en not_active Withdrawn
- 1991-01-17 KR KR1019920701803A patent/KR927003502A/en not_active Application Discontinuation
- 1991-01-17 AU AU70727/91A patent/AU7072791A/en not_active Abandoned
- 1991-01-17 CA CA002074821A patent/CA2074821A1/en not_active Abandoned
- 1991-01-22 ZA ZA91458A patent/ZA91458B/en unknown
- 1991-01-29 CS CS91200A patent/CS20091A2/en unknown
- 1991-01-31 IE IE032991A patent/IE910329A1/en unknown
- 1991-01-31 PT PT96618A patent/PT96618A/en unknown
- 1991-02-01 CN CN91101125A patent/CN1054417A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CS20091A2 (en) | 1991-09-15 |
DE4002988A1 (en) | 1991-08-14 |
CN1054417A (en) | 1991-09-11 |
JPH05503931A (en) | 1993-06-24 |
DE4002988C2 (en) | 1992-01-30 |
AU7072791A (en) | 1991-08-21 |
PT96618A (en) | 1991-10-15 |
ZA91458B (en) | 1991-11-27 |
US5241094A (en) | 1993-08-31 |
EP0513087A1 (en) | 1992-11-19 |
KR927003502A (en) | 1992-12-18 |
IE910329A1 (en) | 1991-08-14 |
WO1991011421A1 (en) | 1991-08-08 |
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