CA2188896A1 - Use of moulding materials to produce moulded articles with good resistance to partially halogenated chlorofluorocarbons - Google Patents
Use of moulding materials to produce moulded articles with good resistance to partially halogenated chlorofluorocarbonsInfo
- Publication number
- CA2188896A1 CA2188896A1 CA002188896A CA2188896A CA2188896A1 CA 2188896 A1 CA2188896 A1 CA 2188896A1 CA 002188896 A CA002188896 A CA 002188896A CA 2188896 A CA2188896 A CA 2188896A CA 2188896 A1 CA2188896 A1 CA 2188896A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- alkyl
- carbon atoms
- acrylonitrile
- styrene
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
The use is disclosed of moulding materials to produce moulded articles which come into contact with partially halogenated chlorofluorocarbons.
Description
~ '` 0050/44830 2 1 8 8 ~ 9 6 ..
U~e of molding materials for the production of molding~ having good resistance to partly halogenated chlorofluorocarbons 5 The present invention relates to the use of certain polymers for the production of moldings which are in contact with partly halo-genated CFCs.
Stress crack-resistant polystyrene and A~S polymers have resis-10 tance to CFCs which is sufficient for most application~ in which corresponding moldings come into direct contact with CFC~.
Refrigerators as used in the private and commercial ~ectors have, as a rule, a sandwich structure comprising a plastic inner con-15 tainer/insulating layer/metal housing. The plaRtic inner contain-ers of these refrigerators are predominantly produced from stre~s crack-resistant polystyrene or A~S polymers. ABS polymers are to be understood as meaning very generally blends of styrene/acrylo-nitrile (SAN) polymers on the one hand and graft copolymer~ hav-20 ing a grafting base comprising butadiene rubbers, onto which theSAN polymers have been grafted.
The plastic inner cont~;ners are produced in general by extrusion and ~ubsequent thermoforming; both proce~ea are known to a per-2S son skilled in the art and are described in the literature. Theplastic inner cont~ner is in direct contact with the insulating layer, which a~ a rule consist~ of polyurethane foam (PUR foam) which is produced using certain blowing agents. While in the past predominantly chlorofluorocarbons (CFCs) were used a~ blowing 30 agents, recently partly halogenated CFCs (HCFCs~, eg. l,l-dichlo-ro-l-fluoroethane (HCFC-141 b), have increasingly been used since they have a less adver~e effect on the protective ozone layer.
However, these novel blowing agents lead to stress cracks, partial di~solution effects and blisters in the case of stress 35 crack-resistant polystyrene as well as A~S polymers, presenting a considerable problem.
JP-A 25227/93 describes thermoplastic molding materials for use as inner lining of refrigerators, which materials contain graft 40 polymer~ which are based on acrylate rubbers and who~e average particle size is at least 150 nm. These are not completely sati~-factory with respect to the weight increase under the action of partly halogenated CFCs.
AMENDED SHEET
~` 0050/44830 .` 2188896 _ 2 It is an object of the present invention to provide products which are suitable for the production of moldings which are in contact with HCFCs, and which have better resistance to these HCFCs than the polymers used to date for such applications.
We have found that this object is achieved, according to the in-vention, by the use as claimed in claim 1.
Preferred embodiments of the invention are described in the sub-10 claims.
Molding materials which can be used according to the invention are those which contain, in component A, a blend of two polymers all) and a12) a~ the grafting base.
The mixing ratio of polymer al1) to al2) is not critical but iB in general from 4:1 to 1:4, in particular from 1:2 to 2:1.
The acrylate polymers a11) are composed of a11l) from 50 to 99.9, preferably from 55 to 98, % by weight of an alkyl acrylate where the alkyl radical is of 1 to 10 carbon atoms. Preferred acrylate~ are those where the alkyl radical i~ of 2 to 10 carbon atoms, in particular ethyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, among which the two last-mentioned are very particularly preferred.
Examples of crossl;nk;ng monomer~ al12), which are used in amounts 30 of from 0.1 to 5, preferably from 0.25 to 4, in particular from 0.5 to 3, % by weight, based on all), are polyfunctional monomers having at lea~t two olefinic, unconjugated double bonds, ~pecific examples of which are divinylbenzene, dialkyl fumarate, diallyl phthalate, triallyl cyanurate, trialkyl isocyanurate, tricyclode-35 cenyl acrylate and dih~dLodicyclopentadienyl acrylate. Tricyclo-decenyl acrylate and dihydrodicyclopentadienyl acrylate are particularly preferred.
Up to 49.9, preferably from 5 to 45, in particular from 10 to 40 40, ~ by weight of monomers which are copolymerizable and tsic]
alll) and are selected from the group consisting of the vinyl al-kyl ethers where the alkyl radical is of 1 to 8 carbon atoms (eg. vinyl methyl ether, vinyl propyl ether, vinyl ethyl ether), butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile 45 and/or methacrylonitrile [sicl may be used as further monomers a1l3) in the preparation of al1).
AMENDED SHEET
,` 0050/44830 ~ 2188896 By using such comonomers, it is possible to control the property profile of the polymers a1l), for example with regard to the de-gree of cro~slinking, which may be desirable in some cases.
5 Processes for the preparation of polymers all) are known to a per-son skilled in the art and are described in the literature, for example in German Patent 1,260,135. Corresponding products are also commercially available.
lO Carrying out the preparation by emulsion polymerization has pro-ven particularly advantageous in some ca~es.
The exact polymerization conditions, in particular the type, dos-age and amount of the emulsifier, are preferably chosen so that 15 the latex of the acrylate, which i9 at least partly crosslinked, has a weight average particle size (d50) of from about 50 to 700 nm, in particular from 100 to 600 nm. The latex preferably has a narrow particle size distribution, ie. the quotient dgo - dlo Q =
d50 25 i9 preferably les~ than 0.5, in particular less than 0.35.
If the grafting base of cc ,onent A consi~ts exclusively of a~
the average particle size of a1l) is less than 150 nm, preferably from 50 to 140 nm, particularly preferably from 50 to 120 nm.
In addition to the polymer~ all), the graft copolymers A) contain butadiene polymers al2) as a second grafting base. The polymers al2) are butadiene copolymers which may also contain to [sic] to 40, preferably from 2 to 30, % by weight of further copolymeriz-35 able monomers in addition to 60-100, preferably 70-99 % by weight of butadiene. The alkyl acrylates described above under a1l1) as well as the monomers a1l3) are suitable as such further copolymer-izable monomers; reference may be made to the description there for details.
The amount of the grafting base all) with al2) in the graft poly-mer A) is from 50 to 90, preferably from 55 to 85, in particular from 60 to 80, % by weight, based on the total weight of A).
45 A graft a2) which is obtained by copolymerization of AMENDED SHEET
-~' 0050/44830 2 ~ 8 8 X 9 6 a2l) from 60 to 90, in particular from 65 to 80, ~ by weight of a vinylaromatic monomer, preferably styrene or a sub~tituted styrene of the general formula I
R--C = CH2 (Rl)n~l where R is alkyl of 1 to 8 carbon atoms, hydrogen or halogen, R1 is alkyl of 1 to 8 carbon atoms or halogen and n i~ 0, 1, 2 or 3, and a22) from 10 to 40, in particular from 20 to 35, $ by weight of polar, copolymerizable monomers [lacuna] acrylonitrile, me-thacrylonitrile, esters of (meth)acrylic acid where the alkyl radical is of 1 to 4 carbon atoms, maleic anhydride, (meth)acrylamide and/or vinyl alkyl ethers where the alkyl r~ al is of 1 to 8 carbon atoms, or of a mixture thereof, is grafted onto the grafting base all) and al2).
The graft a22) may be prepared in one or more, for example two or three, process steps, and the overall composition is not affected 25 thereby.
The graft is preferably prepared in emulsion, as described, for example, in German Patent 1,260,135 and German Laid-Open Applica-tions DOS 3,227,555, DOS 3,149,357, DOS 3,149,358 and 30 DOS 3,414,118.
Depending on the conditions chosen, a certain amount of free co-polymers of styrene and acrylonitrile i8 formed in the graft co-polymerization.
The graft copolymer (al ~ a2) generally has an average particle size of, preferably, from S0 to 1000 nm, in particular from 100 to 700 nm (d50 weight average). The conditions in the preparation of the elastomer bl) and in the grafting are therefore cho~en 90 40 that particle sizes in this range result. Relevant measures are known and are described, for example, in German Patent 1,260,135 and German Laid-Open Application DOS 2,826,925, a~ well a~ in J.
Appl. Polym. Sci. ~ (1965), 2929-2938. The particle size of the latex of the elastomer can be increased, for example, by means of 45 agglomeration.
AMENDED SHEET
' 0050/44830 ~1888~
In some cases, blends of a plurality of acrylate polymers which have different particle sizes have also proven useful. Corre-sponding products are described in German Laid-Open Application DOS 2,826,925 and U.S. Patent 5,196,480, to which reference is 5 made here for further details.
Accordingly, preferably used blends of acrylate polymers are those in which a fir~t polymer has a particle size d50 of from 50 to 150 nm and a ~econd polymer has a particle size of from 200 to 10 700 nm, as described in the abovementioned U.S. Patent 5,196,480.
In the blends of polymers all) (as described in German Publi~hed Application DAS 1,164,080, German Patent 1,911,882 and German Laid-Open Application DOS 3,149,358) and polymers al2), the 15 polymers al2) in general have an average particle size of from 50 to 1000 nm, preferably from 100 to 700 nm.
Some preferred graft polymers all) are shown below:
20 a2/l: 60 % by weight of grafting base a2l) comprising a2ll) 98 % by weight of n-butyl acrylate and a2l2) 2 % by weight of dihydrodicyclopentadienyl acrylate and 40 % by weight of graft a22) comprising a22l) 75 % by weight of styrene and a222) 25 % by weight of acrylonitrile a2/2: grafting base as in a2/l with 5 % by weight of a graft comprising a22l) 12.5 % by weight of styrene (l~t graft stage) and 40 % by weight of a second graft stage comprising a22l) 75 % by weight of styrene and a222) 25 % by weight of acrylonitrile a3/2: grafting ba~e as in a2/l with 13 % by weight of a first graft stage compri~ing styrene and 27 % by weight of a second graft stage comprising styrene and acrylonitrile in a weight ratio 3:1.
The novel molding materials contain, as component B), from 30 to 40 99, preferably from 40 to 80, % by weight of a copolymer of b1) from 50 to 90, preferably from 55 to 90, in particular from 65 to 85, % Dy weight of vinylaromatic monomers, preferably ~tyrene and/or substituted styrenes of the general formul,a I and - AMENDED SHEET
~ 0050/44830 "` . 2i8~8g6 __ 6 b2) from 1~ to 50, preferably from 10 to 45, in particular from 15 to 35, % by weight of the monomers described for a22).
Such products can be prepared, for example, by the process de-5 scribed in German Published Applications DAS 1,001,001 and DAS 1,003,436. Such copolymers are also commercially available.
The weight average molecular weight determined by light scattering is preferably from 50,000 to 500,000, in particular from 100,000 to 250,000, corresponding to viscosity numbers of 10 from 30 to 130, preferably from 30 to 100 (measured in 0.5 %
strength by weight solution in dimethylformamide at 25 C).
Up to 20, preferably from 0.5 to 10, % by weight of conventional additives and processing assistants may be present as compo-15 nent C.
Conventional additives are, for example, stabilizers and anti-oxidants, heat 6tabilizers and W stabilizers, lubricants and mold release agents, colorants, such as dyes and pigments, pul-20 verulent fillers and reinforcing agents, and plasticizers. Suchadditives are used in the conventional effective amounts.
The stabilizers may be added to the materials at any stage of the preparation of the the ~la~tic material~. The stabilizers are 25 preferably added at an early stage in order to prevent decomposi-tion from beginning before the material can be protected. Such stabilizers must be compatible with the material.
The antioxidants and heat stabilizers which may be added to the 30 thermoplastic material~ according to the invention include those which are generally added to polymers, such as halides of metals of group I of the Periodic Table, for example sodium halides, po-tassium halides and lithium halides in combination with copper(I) halides, for example chloride, bromide or iodide. Other suitable 35 stabilizers are sterically hin~ered phenols, hydroquinones, various substituted members of this group around [sic] combina-tions thereof, in concentrations of up to 1 % by weight, based on the weight of the mixture.
40 Stabilizers which are generally added to polymers may also be used as stabilizers, in amounts of up 2.0 % by weight, tlacuna]
on the mixture.
AMENDED SHEET
, 0050/44830 ~1~8g96 Examples of stabilizers are various substituted resorcinols, sal-icylates, benzotriazoles, benzophenones, HALS stabilizers and the like, as commercially available under the tradenames Topanol~, Irganox~ and Tinuvin~.
Suitable lubricants and mold release agents, which are added, for example, in amounts of up to 1 % by weight of the thermoplastic material, are stearic acids, ~tearyl alcohol, stearic esters and stearamides.
Further possible additives are silicone oils, preferably in amount~ of from 0.05 to 1 % by weight.
Organic dyes, such as nigrosine, and pigments, eg. titanium diox-lS ide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black, may also be added.
According to the invention, the molding materials described above are used for the production of moldings which come into contact 20 with partly halogenated CFCs ~ie. HCFCs). Two known members of this class of substances are 1,1-dichloro-1-fluoroethane (HCFC
141 b) and 1,1-dichloro-2,2,2-trifluoroethane (HCFC 123).
The moldings can be pLoduced by methods which are known per se to 25 a person skilled in the art and are described in the literature, such as extrusion, injection molding, blow molding and thermo-forming, to mention but a few.
The moldings obt~in~hle according to the invention possess good 30 stress cracking resistance and good resistance to complete lsic]
dissolution by HCFCs in addition to good processability and are therefore suitable for all applications in contact with HCFCs, in particular for the production of inner containers in refrigera-tors.
Examples The following o~ ~,onents were used:
40 Al: graft polymer of % by weight of a grafting base comprising 98 % by weight of n-butyl acrylate and 2 % by weight of dihydrodicyclopentadienyl acrylate and 4S 40 % by weight of a graft comprising a copolymer AMENDED SHEET
~ ` 0050/44830 ~1~889G
of 75 % by weight of styrene and 25 % by weight of acrylonitrile having an average particle diameter d50 of 100 nm 5 A2: graft copolymer of % by weight of a grafting base as in A
and % by weight of a graft comprising % by weight of styrene and 30 % by weight of acrylonitrile, having an average particle diameter d50 of 250-350 nm A3: graft copolymer of 60 % by weight of a grafting base as in Al and A2, 13 % by weight of a first graft comprising styrene and 27 % by weight of a second graft comprising a copolymer of 75 % by weight of styrene and 25 % by weight of acrylonitrile, having an average particle diameter d50 of 500 nm A4: graft copolymer of 62 % by weight of a grafting base comprising butadiene and 38 % by weight of a graft comprising 70 % by weight of styrene and 30 % by weight of acrylonitrile A5: graft copolymer contAi n; ng 62 % by weight of a grafting base as in A5, 13 % by weight of a first graft comprising styrene and % by weight of a second graft compri~ing 70 % by weight of styrene and 30 % by weight of acrylonitrile B1: copolymer of 65 % by weight of styrene and 35 % by weight of acrylonitrile, having a vi~cosity number (VN) of 80 ml/g, measured in 0.5 % ~trength by weight solution in dimethyl-formamide at 25C
B2: copolymer having the same compo~ition as Bl, but a viscosity number of 60 ml/g Cl: diisode~yl phthalate (Palatinol~Z from BASF
Aktiengesellschaft) C2: 1,1,3-tri(2'-methyl-4'-hydroxin-5'-tert-butylphenyl)butane tsiC] (Topanol~ CA from ICI) - AMENDED SHEET
`` 2188~96 g C3: dilauryl ~ thiodipropionate (Irganox~ PS 800 from Ciba-Geigy AG) C4: n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propane (Irganox~ 1076 from Ciba-Geigy AG) Components A, B and C were mixed in an extruder in the amounts stated in the table, the mixture was extruded and the extrudate granulated. In order to determine the stress cracking resistance 10 and the partial dissolution behavior, test specimens and sheets were produced from the granules by compression molding or by in-jection molding.
The Steinle test is used for determining the stress cracking re-15 sistance of the products with respect to HCFC 123. To carry out the test, compression molded or injection molded dumbbells are clamped over a bending radius of 170 mm and stored in an HCFC 123 atmosphere at 0.5 bar for 10 minutes and 50 minutes. The tensile test according to DIN 53 455 is carried out immediately there-20 after. Any stress cracks which occur in the material manifestthemselves in a sharp decrease in the elongation at break. The corresponding values are shown in the table.
In order to test the resistance of the materials to partial dis-25 solution, a special test was developed. The test specimens used are compression molded sheets having a thickness of about 0.5 mm.
These are fastened, with a 2 mm thick intermediate polythene layer, to a metal sheet. The arrangement, with the test sheet facing downward, is placed on a vessel which is filled with the 30 blowing agent (HCFC). Solid carbon dioxide is present on the met-al sheet, so that the rising HCFC 123 vapors condense on the plastic sheet. The intermediate polyethylene layer prevents the presence of a diffusion barrier behind the test specimen.
35 After an action time of 1 hour, disks having a diameter of about 2.7 cm are punched out of the plastic sheet, dried in the air for 10 minutes and then weighed. The drying time in the air ensures that blowing agent present on the sheet can evaporate off. The sheets are dried for 24 hours at 40-C and then weighed again. The ~0 difference gives the amount of blowing agent absorbed.
The blistering is assessed visually.
The results are shown in the table.
AMENDED SHEET
~ ` ' 0050/44830 2 1 ~ 8 ~9 6 c~_ m ,C
o o n.
r_ .
U~e of molding materials for the production of molding~ having good resistance to partly halogenated chlorofluorocarbons 5 The present invention relates to the use of certain polymers for the production of moldings which are in contact with partly halo-genated CFCs.
Stress crack-resistant polystyrene and A~S polymers have resis-10 tance to CFCs which is sufficient for most application~ in which corresponding moldings come into direct contact with CFC~.
Refrigerators as used in the private and commercial ~ectors have, as a rule, a sandwich structure comprising a plastic inner con-15 tainer/insulating layer/metal housing. The plaRtic inner contain-ers of these refrigerators are predominantly produced from stre~s crack-resistant polystyrene or A~S polymers. ABS polymers are to be understood as meaning very generally blends of styrene/acrylo-nitrile (SAN) polymers on the one hand and graft copolymer~ hav-20 ing a grafting base comprising butadiene rubbers, onto which theSAN polymers have been grafted.
The plastic inner cont~;ners are produced in general by extrusion and ~ubsequent thermoforming; both proce~ea are known to a per-2S son skilled in the art and are described in the literature. Theplastic inner cont~ner is in direct contact with the insulating layer, which a~ a rule consist~ of polyurethane foam (PUR foam) which is produced using certain blowing agents. While in the past predominantly chlorofluorocarbons (CFCs) were used a~ blowing 30 agents, recently partly halogenated CFCs (HCFCs~, eg. l,l-dichlo-ro-l-fluoroethane (HCFC-141 b), have increasingly been used since they have a less adver~e effect on the protective ozone layer.
However, these novel blowing agents lead to stress cracks, partial di~solution effects and blisters in the case of stress 35 crack-resistant polystyrene as well as A~S polymers, presenting a considerable problem.
JP-A 25227/93 describes thermoplastic molding materials for use as inner lining of refrigerators, which materials contain graft 40 polymer~ which are based on acrylate rubbers and who~e average particle size is at least 150 nm. These are not completely sati~-factory with respect to the weight increase under the action of partly halogenated CFCs.
AMENDED SHEET
~` 0050/44830 .` 2188896 _ 2 It is an object of the present invention to provide products which are suitable for the production of moldings which are in contact with HCFCs, and which have better resistance to these HCFCs than the polymers used to date for such applications.
We have found that this object is achieved, according to the in-vention, by the use as claimed in claim 1.
Preferred embodiments of the invention are described in the sub-10 claims.
Molding materials which can be used according to the invention are those which contain, in component A, a blend of two polymers all) and a12) a~ the grafting base.
The mixing ratio of polymer al1) to al2) is not critical but iB in general from 4:1 to 1:4, in particular from 1:2 to 2:1.
The acrylate polymers a11) are composed of a11l) from 50 to 99.9, preferably from 55 to 98, % by weight of an alkyl acrylate where the alkyl radical is of 1 to 10 carbon atoms. Preferred acrylate~ are those where the alkyl radical i~ of 2 to 10 carbon atoms, in particular ethyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, among which the two last-mentioned are very particularly preferred.
Examples of crossl;nk;ng monomer~ al12), which are used in amounts 30 of from 0.1 to 5, preferably from 0.25 to 4, in particular from 0.5 to 3, % by weight, based on all), are polyfunctional monomers having at lea~t two olefinic, unconjugated double bonds, ~pecific examples of which are divinylbenzene, dialkyl fumarate, diallyl phthalate, triallyl cyanurate, trialkyl isocyanurate, tricyclode-35 cenyl acrylate and dih~dLodicyclopentadienyl acrylate. Tricyclo-decenyl acrylate and dihydrodicyclopentadienyl acrylate are particularly preferred.
Up to 49.9, preferably from 5 to 45, in particular from 10 to 40 40, ~ by weight of monomers which are copolymerizable and tsic]
alll) and are selected from the group consisting of the vinyl al-kyl ethers where the alkyl radical is of 1 to 8 carbon atoms (eg. vinyl methyl ether, vinyl propyl ether, vinyl ethyl ether), butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile 45 and/or methacrylonitrile [sicl may be used as further monomers a1l3) in the preparation of al1).
AMENDED SHEET
,` 0050/44830 ~ 2188896 By using such comonomers, it is possible to control the property profile of the polymers a1l), for example with regard to the de-gree of cro~slinking, which may be desirable in some cases.
5 Processes for the preparation of polymers all) are known to a per-son skilled in the art and are described in the literature, for example in German Patent 1,260,135. Corresponding products are also commercially available.
lO Carrying out the preparation by emulsion polymerization has pro-ven particularly advantageous in some ca~es.
The exact polymerization conditions, in particular the type, dos-age and amount of the emulsifier, are preferably chosen so that 15 the latex of the acrylate, which i9 at least partly crosslinked, has a weight average particle size (d50) of from about 50 to 700 nm, in particular from 100 to 600 nm. The latex preferably has a narrow particle size distribution, ie. the quotient dgo - dlo Q =
d50 25 i9 preferably les~ than 0.5, in particular less than 0.35.
If the grafting base of cc ,onent A consi~ts exclusively of a~
the average particle size of a1l) is less than 150 nm, preferably from 50 to 140 nm, particularly preferably from 50 to 120 nm.
In addition to the polymer~ all), the graft copolymers A) contain butadiene polymers al2) as a second grafting base. The polymers al2) are butadiene copolymers which may also contain to [sic] to 40, preferably from 2 to 30, % by weight of further copolymeriz-35 able monomers in addition to 60-100, preferably 70-99 % by weight of butadiene. The alkyl acrylates described above under a1l1) as well as the monomers a1l3) are suitable as such further copolymer-izable monomers; reference may be made to the description there for details.
The amount of the grafting base all) with al2) in the graft poly-mer A) is from 50 to 90, preferably from 55 to 85, in particular from 60 to 80, % by weight, based on the total weight of A).
45 A graft a2) which is obtained by copolymerization of AMENDED SHEET
-~' 0050/44830 2 ~ 8 8 X 9 6 a2l) from 60 to 90, in particular from 65 to 80, ~ by weight of a vinylaromatic monomer, preferably styrene or a sub~tituted styrene of the general formula I
R--C = CH2 (Rl)n~l where R is alkyl of 1 to 8 carbon atoms, hydrogen or halogen, R1 is alkyl of 1 to 8 carbon atoms or halogen and n i~ 0, 1, 2 or 3, and a22) from 10 to 40, in particular from 20 to 35, $ by weight of polar, copolymerizable monomers [lacuna] acrylonitrile, me-thacrylonitrile, esters of (meth)acrylic acid where the alkyl radical is of 1 to 4 carbon atoms, maleic anhydride, (meth)acrylamide and/or vinyl alkyl ethers where the alkyl r~ al is of 1 to 8 carbon atoms, or of a mixture thereof, is grafted onto the grafting base all) and al2).
The graft a22) may be prepared in one or more, for example two or three, process steps, and the overall composition is not affected 25 thereby.
The graft is preferably prepared in emulsion, as described, for example, in German Patent 1,260,135 and German Laid-Open Applica-tions DOS 3,227,555, DOS 3,149,357, DOS 3,149,358 and 30 DOS 3,414,118.
Depending on the conditions chosen, a certain amount of free co-polymers of styrene and acrylonitrile i8 formed in the graft co-polymerization.
The graft copolymer (al ~ a2) generally has an average particle size of, preferably, from S0 to 1000 nm, in particular from 100 to 700 nm (d50 weight average). The conditions in the preparation of the elastomer bl) and in the grafting are therefore cho~en 90 40 that particle sizes in this range result. Relevant measures are known and are described, for example, in German Patent 1,260,135 and German Laid-Open Application DOS 2,826,925, a~ well a~ in J.
Appl. Polym. Sci. ~ (1965), 2929-2938. The particle size of the latex of the elastomer can be increased, for example, by means of 45 agglomeration.
AMENDED SHEET
' 0050/44830 ~1888~
In some cases, blends of a plurality of acrylate polymers which have different particle sizes have also proven useful. Corre-sponding products are described in German Laid-Open Application DOS 2,826,925 and U.S. Patent 5,196,480, to which reference is 5 made here for further details.
Accordingly, preferably used blends of acrylate polymers are those in which a fir~t polymer has a particle size d50 of from 50 to 150 nm and a ~econd polymer has a particle size of from 200 to 10 700 nm, as described in the abovementioned U.S. Patent 5,196,480.
In the blends of polymers all) (as described in German Publi~hed Application DAS 1,164,080, German Patent 1,911,882 and German Laid-Open Application DOS 3,149,358) and polymers al2), the 15 polymers al2) in general have an average particle size of from 50 to 1000 nm, preferably from 100 to 700 nm.
Some preferred graft polymers all) are shown below:
20 a2/l: 60 % by weight of grafting base a2l) comprising a2ll) 98 % by weight of n-butyl acrylate and a2l2) 2 % by weight of dihydrodicyclopentadienyl acrylate and 40 % by weight of graft a22) comprising a22l) 75 % by weight of styrene and a222) 25 % by weight of acrylonitrile a2/2: grafting base as in a2/l with 5 % by weight of a graft comprising a22l) 12.5 % by weight of styrene (l~t graft stage) and 40 % by weight of a second graft stage comprising a22l) 75 % by weight of styrene and a222) 25 % by weight of acrylonitrile a3/2: grafting ba~e as in a2/l with 13 % by weight of a first graft stage compri~ing styrene and 27 % by weight of a second graft stage comprising styrene and acrylonitrile in a weight ratio 3:1.
The novel molding materials contain, as component B), from 30 to 40 99, preferably from 40 to 80, % by weight of a copolymer of b1) from 50 to 90, preferably from 55 to 90, in particular from 65 to 85, % Dy weight of vinylaromatic monomers, preferably ~tyrene and/or substituted styrenes of the general formul,a I and - AMENDED SHEET
~ 0050/44830 "` . 2i8~8g6 __ 6 b2) from 1~ to 50, preferably from 10 to 45, in particular from 15 to 35, % by weight of the monomers described for a22).
Such products can be prepared, for example, by the process de-5 scribed in German Published Applications DAS 1,001,001 and DAS 1,003,436. Such copolymers are also commercially available.
The weight average molecular weight determined by light scattering is preferably from 50,000 to 500,000, in particular from 100,000 to 250,000, corresponding to viscosity numbers of 10 from 30 to 130, preferably from 30 to 100 (measured in 0.5 %
strength by weight solution in dimethylformamide at 25 C).
Up to 20, preferably from 0.5 to 10, % by weight of conventional additives and processing assistants may be present as compo-15 nent C.
Conventional additives are, for example, stabilizers and anti-oxidants, heat 6tabilizers and W stabilizers, lubricants and mold release agents, colorants, such as dyes and pigments, pul-20 verulent fillers and reinforcing agents, and plasticizers. Suchadditives are used in the conventional effective amounts.
The stabilizers may be added to the materials at any stage of the preparation of the the ~la~tic material~. The stabilizers are 25 preferably added at an early stage in order to prevent decomposi-tion from beginning before the material can be protected. Such stabilizers must be compatible with the material.
The antioxidants and heat stabilizers which may be added to the 30 thermoplastic material~ according to the invention include those which are generally added to polymers, such as halides of metals of group I of the Periodic Table, for example sodium halides, po-tassium halides and lithium halides in combination with copper(I) halides, for example chloride, bromide or iodide. Other suitable 35 stabilizers are sterically hin~ered phenols, hydroquinones, various substituted members of this group around [sic] combina-tions thereof, in concentrations of up to 1 % by weight, based on the weight of the mixture.
40 Stabilizers which are generally added to polymers may also be used as stabilizers, in amounts of up 2.0 % by weight, tlacuna]
on the mixture.
AMENDED SHEET
, 0050/44830 ~1~8g96 Examples of stabilizers are various substituted resorcinols, sal-icylates, benzotriazoles, benzophenones, HALS stabilizers and the like, as commercially available under the tradenames Topanol~, Irganox~ and Tinuvin~.
Suitable lubricants and mold release agents, which are added, for example, in amounts of up to 1 % by weight of the thermoplastic material, are stearic acids, ~tearyl alcohol, stearic esters and stearamides.
Further possible additives are silicone oils, preferably in amount~ of from 0.05 to 1 % by weight.
Organic dyes, such as nigrosine, and pigments, eg. titanium diox-lS ide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black, may also be added.
According to the invention, the molding materials described above are used for the production of moldings which come into contact 20 with partly halogenated CFCs ~ie. HCFCs). Two known members of this class of substances are 1,1-dichloro-1-fluoroethane (HCFC
141 b) and 1,1-dichloro-2,2,2-trifluoroethane (HCFC 123).
The moldings can be pLoduced by methods which are known per se to 25 a person skilled in the art and are described in the literature, such as extrusion, injection molding, blow molding and thermo-forming, to mention but a few.
The moldings obt~in~hle according to the invention possess good 30 stress cracking resistance and good resistance to complete lsic]
dissolution by HCFCs in addition to good processability and are therefore suitable for all applications in contact with HCFCs, in particular for the production of inner containers in refrigera-tors.
Examples The following o~ ~,onents were used:
40 Al: graft polymer of % by weight of a grafting base comprising 98 % by weight of n-butyl acrylate and 2 % by weight of dihydrodicyclopentadienyl acrylate and 4S 40 % by weight of a graft comprising a copolymer AMENDED SHEET
~ ` 0050/44830 ~1~889G
of 75 % by weight of styrene and 25 % by weight of acrylonitrile having an average particle diameter d50 of 100 nm 5 A2: graft copolymer of % by weight of a grafting base as in A
and % by weight of a graft comprising % by weight of styrene and 30 % by weight of acrylonitrile, having an average particle diameter d50 of 250-350 nm A3: graft copolymer of 60 % by weight of a grafting base as in Al and A2, 13 % by weight of a first graft comprising styrene and 27 % by weight of a second graft comprising a copolymer of 75 % by weight of styrene and 25 % by weight of acrylonitrile, having an average particle diameter d50 of 500 nm A4: graft copolymer of 62 % by weight of a grafting base comprising butadiene and 38 % by weight of a graft comprising 70 % by weight of styrene and 30 % by weight of acrylonitrile A5: graft copolymer contAi n; ng 62 % by weight of a grafting base as in A5, 13 % by weight of a first graft comprising styrene and % by weight of a second graft compri~ing 70 % by weight of styrene and 30 % by weight of acrylonitrile B1: copolymer of 65 % by weight of styrene and 35 % by weight of acrylonitrile, having a vi~cosity number (VN) of 80 ml/g, measured in 0.5 % ~trength by weight solution in dimethyl-formamide at 25C
B2: copolymer having the same compo~ition as Bl, but a viscosity number of 60 ml/g Cl: diisode~yl phthalate (Palatinol~Z from BASF
Aktiengesellschaft) C2: 1,1,3-tri(2'-methyl-4'-hydroxin-5'-tert-butylphenyl)butane tsiC] (Topanol~ CA from ICI) - AMENDED SHEET
`` 2188~96 g C3: dilauryl ~ thiodipropionate (Irganox~ PS 800 from Ciba-Geigy AG) C4: n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propane (Irganox~ 1076 from Ciba-Geigy AG) Components A, B and C were mixed in an extruder in the amounts stated in the table, the mixture was extruded and the extrudate granulated. In order to determine the stress cracking resistance 10 and the partial dissolution behavior, test specimens and sheets were produced from the granules by compression molding or by in-jection molding.
The Steinle test is used for determining the stress cracking re-15 sistance of the products with respect to HCFC 123. To carry out the test, compression molded or injection molded dumbbells are clamped over a bending radius of 170 mm and stored in an HCFC 123 atmosphere at 0.5 bar for 10 minutes and 50 minutes. The tensile test according to DIN 53 455 is carried out immediately there-20 after. Any stress cracks which occur in the material manifestthemselves in a sharp decrease in the elongation at break. The corresponding values are shown in the table.
In order to test the resistance of the materials to partial dis-25 solution, a special test was developed. The test specimens used are compression molded sheets having a thickness of about 0.5 mm.
These are fastened, with a 2 mm thick intermediate polythene layer, to a metal sheet. The arrangement, with the test sheet facing downward, is placed on a vessel which is filled with the 30 blowing agent (HCFC). Solid carbon dioxide is present on the met-al sheet, so that the rising HCFC 123 vapors condense on the plastic sheet. The intermediate polyethylene layer prevents the presence of a diffusion barrier behind the test specimen.
35 After an action time of 1 hour, disks having a diameter of about 2.7 cm are punched out of the plastic sheet, dried in the air for 10 minutes and then weighed. The drying time in the air ensures that blowing agent present on the sheet can evaporate off. The sheets are dried for 24 hours at 40-C and then weighed again. The ~0 difference gives the amount of blowing agent absorbed.
The blistering is assessed visually.
The results are shown in the table.
AMENDED SHEET
~ ` ' 0050/44830 2 1 ~ 8 ~9 6 c~_ m ,C
o o n.
r_ .
3~
r ~ ~ ~ ~D
.~ ~ ~1 ,,~
O
O ~_ O
O O O O O O U~
~ 0~
~ ~ ~ t ~ , N :
~-1 0 0 --I I ~
g on.C m m m m m U U~ m m~
v ,- 3 U~ o o 1` r` ~o O m ~_ ~ X
~¢ . p, ~I _ O
~ I ~P P ~ p ~
r ~ ~ ~ ~D
.~ ~ ~1 ,,~
O
O ~_ O
O O O O O O U~
~ 0~
~ ~ ~ t ~ , N :
~-1 0 0 --I I ~
g on.C m m m m m U U~ m m~
v ,- 3 U~ o o 1` r` ~o O m ~_ ~ X
~¢ . p, ~I _ O
~ I ~P P ~ p ~
Claims (2)
1. Use of a molding material containing, as essential compo-nents, A) from 1 to 50 % by weight, based on the total weight of the molding material, of a graft copolymer composed of a1) from 50 to 90 % by weight, based on A), of a grafting base composed of a11) a partially or completely crosslinked acrylate polymer formed from a111) from 50 to 99.9 % by weight, based on a11), of at least one alkyl acrylate where the alkyl radical is of 1 to 10 carbon atoms, a112) from 0.1 to 5 % by weight, based on a11), of a polyfunctional, crosslinking monomer and a113) from 0 to 49.9 % by weight, based on a11), of a further monomer which is copolymeriz-able with a111) and is selected from the group consisting of the vinyl alkyl ethers where the alkyl radical is of 1 to 8 car-bon atoms, butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile and methyl methacrylate and a12) a butadiene polymer composed of a121) from 60 to 100 % by weight, based on a12), of butadiene, and a122) from 0 to 40 % by weight, based on a12) of further copolymerizable monomers selected from the group consisting of the vinyl alkyl ethers where the alkyl group is of 1 to 8 carbon atoms, alkyl acrylates where the alkyl group is of 1 to 10 carbon atoms, isoprene, styrene, acrylonitrile, methacrylonitrile and methyl methacrylate and a2) from 10 to 50 % by weight, based on A), of a shell grafted onto the graft copolymer and composed of a21) from 50 to 95 % by weight, based on a21), of a vinylaromatic monomer and a22) from 5 to 50 % by weight of polar, copolymeriz-able comonomers selected from the group consis-ting of acrylonitrile, methacrylonitrile, esters of (meth)acrylic acid where the alkyl radical is of 1 to 4 carbon atoms, maleic anhydride, (meth)acrylamide and vinyl alkyl ethers where the alkyl radical is of 1 to 8 carbon atoms, B) from 30 to 99 % by weight, based on the total weight of the molding material, of a copolymer of b1) from 50 to 99 % by weight of a vinylaromatic monomer and b2) from 1 to 50 % by weight of monomers as described for a22) and C) from 0 to 20 % by weight of conventional additives and processing assistants for the production of moldings which come into contact with partly halogenated CFCs (HCFCs), with the proviso that the weight average particle size (d50) of the component a11) is less than 150 nm if the component A contains only a11) as the grafting base.
2. Use as claimed in claim 1 for the production of inner con-tainers in refrigerators.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4414417.2 | 1994-04-25 | ||
| DE4414417 | 1994-04-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2188896A1 true CA2188896A1 (en) | 1995-11-02 |
Family
ID=6516392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002188896A Abandoned CA2188896A1 (en) | 1994-04-25 | 1995-04-24 | Use of moulding materials to produce moulded articles with good resistance to partially halogenated chlorofluorocarbons |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0757706B1 (en) |
| JP (1) | JPH09512293A (en) |
| KR (1) | KR970702322A (en) |
| CN (1) | CN1054388C (en) |
| AU (1) | AU688905B2 (en) |
| CA (1) | CA2188896A1 (en) |
| DE (1) | DE59503174D1 (en) |
| ES (1) | ES2119439T3 (en) |
| MY (1) | MY130535A (en) |
| TW (1) | TW282483B (en) |
| WO (1) | WO1995029204A1 (en) |
| ZA (1) | ZA953281B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569845C (en) * | 2002-11-21 | 2009-12-16 | 大科能树脂有限公司 | Thermoplastic resin composition, vehicle exterior equipment are adornd with moulding product and manufacture method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US229457A (en) * | 1880-06-29 | phillips | ||
| JPS525227A (en) * | 1975-07-01 | 1977-01-14 | Mitsubishi Electric Corp | Input/output command re-try |
| JP3090942B2 (en) * | 1990-11-02 | 2000-09-25 | 三菱化学株式会社 | Thermoplastic resin composition for refrigerator inner box and refrigerator inner box obtained by molding the same |
| JPH0525227A (en) * | 1991-07-23 | 1993-02-02 | Mitsubishi Rayon Co Ltd | Thermoplastic resin |
| US20050281414A1 (en) * | 2004-06-18 | 2005-12-22 | Simon Gregory R | Method and apparatus for control of personal digital media devices using a vehicle audio system |
-
1995
- 1995-04-20 TW TW084103898A patent/TW282483B/zh active
- 1995-04-22 MY MYPI95001054A patent/MY130535A/en unknown
- 1995-04-24 KR KR1019960705969A patent/KR970702322A/en not_active Application Discontinuation
- 1995-04-24 ZA ZA953281A patent/ZA953281B/en unknown
- 1995-04-24 AU AU24478/95A patent/AU688905B2/en not_active Ceased
- 1995-04-24 CA CA002188896A patent/CA2188896A1/en not_active Abandoned
- 1995-04-24 WO PCT/EP1995/001535 patent/WO1995029204A1/en active IP Right Grant
- 1995-04-24 EP EP95918594A patent/EP0757706B1/en not_active Expired - Lifetime
- 1995-04-24 DE DE59503174T patent/DE59503174D1/en not_active Expired - Lifetime
- 1995-04-24 CN CN95193194A patent/CN1054388C/en not_active Expired - Fee Related
- 1995-04-24 JP JP7527359A patent/JPH09512293A/en active Pending
- 1995-04-24 ES ES95918594T patent/ES2119439T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU688905B2 (en) | 1998-03-19 |
| EP0757706B1 (en) | 1998-08-12 |
| CN1149306A (en) | 1997-05-07 |
| CN1054388C (en) | 2000-07-12 |
| TW282483B (en) | 1996-08-01 |
| KR970702322A (en) | 1997-05-13 |
| WO1995029204A1 (en) | 1995-11-02 |
| ES2119439T3 (en) | 1998-10-01 |
| DE59503174D1 (en) | 1998-09-17 |
| ZA953281B (en) | 1996-10-24 |
| EP0757706A1 (en) | 1997-02-12 |
| MY130535A (en) | 2007-06-29 |
| AU2447895A (en) | 1995-11-16 |
| JPH09512293A (en) | 1997-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2012062479A (en) | Electrostatic-dissipative multipolymer composition | |
| KR100649512B1 (en) | Thermoplastic Moulding Materials for Internal Applications in a Motor Vehicle | |
| US11505688B2 (en) | Scratch-resistant styrene copolymer composition containing modified organopolysiloxane compounds | |
| WO1992013917A1 (en) | Transparent high impact alloy | |
| EP0037609B1 (en) | Impact resistant polymer composition | |
| CA2188896A1 (en) | Use of moulding materials to produce moulded articles with good resistance to partially halogenated chlorofluorocarbons | |
| JPH10298397A (en) | Styrene-based resin composition | |
| KR100651620B1 (en) | Improved flow carbonate polymer blends and method for preparing the same | |
| JP2004042360A (en) | Transparent sheet excellent in antistaticity and its molding | |
| JP4318783B2 (en) | Rubber-modified styrenic resin composition and sheet thereof | |
| JP2004339442A (en) | Resin composition and lamp lens for vehicle produced by using the same | |
| CA2115950C (en) | Highly transparent tough polymer blends | |
| JPH05279549A (en) | Flame-retardant thermoplastic resin composition | |
| JP2002201324A (en) | Resin composition, heat-shrinkable film and heat- shrinkable multilayer film | |
| JPH1087759A (en) | Rubber modified styrene-based resin and its composition | |
| JPH09227738A (en) | Aromatic vinyl-based resin composition | |
| WO2008042582A2 (en) | Polymer blend composition and articles thereof | |
| JPH11147920A (en) | Rubber-modified styrene polymer | |
| KR100449059B1 (en) | Rubber modified syrene-based resin composition and formed article thereof | |
| MXPA96005116A (en) | Use of molding materials for the production of molded pieces that have a good resistance to partially halogenic chlorofluorocarbons | |
| JPH09278960A (en) | Styrene resin composition | |
| JP2001131298A (en) | Molded article of rubber modified styrenic polymer | |
| EP0052872A2 (en) | Blends of vinyl chloride polymer and graft copolymer composition | |
| JPH07324149A (en) | Styrene resin composition | |
| JPS6137836A (en) | Matte thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |