Compositions, containing thermoplastics based on polyvinyl chloride and containing cross-linked NBR microgels modified with hydroxyl groups
The present invention relates to a composition obtainable by mixing to incorporate at least one microgel (B) that has been crosslinked by means of free-radical generators photochemical by using a wavelength>0.1 μm and/or thermally and that contains hydroxy groups and that is based on polybutadiene-acrylonitrile copolymers (NBR) into polyvinyl chloride (PVC) in an extruder, to processes for production thereof and to use thereof for reproduction of transparent thermoplastically processable molded items, and also to molded items produced from the said compositions.
1. A composition comprising:
at least one polyvinyl chloride thermoplastic, and
at least one microgel comprising at least one of: a crosslinked polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups, and a crosslinked, carboxylated, polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups, wherein the microgel is thermally cross-linked using organic peroxides, as thermal free-radical initiator.
2. The composition according to claim 1 , wherein the microgel contains individual primary particles, and the deviation of the diameters of an individual primary particle of the microgel, defined as
[( d 1− d 2)/ d 2]×100%
is smaller than 500%, where d1 and d2 are diameters of the primary particle with the proviso that d1 is >d2.
3. The composition according to claim 1 , wherein the median particle size d 50 of the primary particles of the microgel is 5 to 500 nm.
4. The composition according to claim 1 , wherein the crosslinked polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups, and the crosslinked, carboxylated, polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups each have an acrylonitrile content of 10% to 80%.
5. The composition according to claim 1 , wherein the microgel comprises at least about 70% by weight of fractions insoluble in toluene at 23° C.
6. The composition according to claim 1 , wherein:
the swelling index of the microgel in toluene at 23° C. is less than about 80;
the glass transition temperature of the microgel is from −60° C. to +50° C.; and
the breadth of the glass transition range of the microgel is greater than about 5° C.
7. The composition according to claim 1 , wherein the microgel is cross-linked using trimethylolpropane trimethacrylate (TMPTMA).
8. The composition according to claim 1 , the composition has a thermoplastic/microgel ratio by weight of 99:1 to 60:40.
9. The composition according to claim 1 , produced by a method comprising mixing the at least one polyvinyl chloride and the at least one microgel.
10. A process for the production of the composition according to claim 1 , the process comprising:
crosslinking the at least one microgel thermally using organic peroxides to produce at least one crosslinked microgel; and
mixing the at least one polyvinyl chloride and the at least one crosslinked microgel.
11. A masterbatch for thermoplastic materials, the masterbatch comprising a composition according to claim 1 .
12. Moulded items obtained via moulding of a composition according to claim 1 .
13. The composition according to claim 1 , wherein:
the microgel contains individual primary particles, and the deviation of the diameters of an individual primary particle of the microgel, defined as [(d1−d2)/d2]×100%, where d1 and d2 are diameters of the primary particle with the proviso that d1 is >d2, is smaller than 500%;
the median particle size d 50 of the primary particles of the microgel is 5 to 500 nm;
the crosslinked polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups, and the crosslinked carboxylated, polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups each have an acrylonitrile content of 10% to 80%;
the microgel comprises at least about 70% by weight of fractions insoluble in toluene at 23° C.;
the swelling index of the microgel in toluene at 23° C. is less than about 80;
the glass transition temperature of the microgel is from −60° C. to +50° C.;
the breadth of the glass transition range of the microgel is greater than about 5° C.; and
the composition has a thermoplastic/microgel ratio by weight of 99:1 to 60:40.
14. The composition according to claim 13 , wherein:
the acrylonitrile content of the crosslinked polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups, and the crosslinked, carboxylated, polybutadiene-acrylonitrile copolymer microgel that contains hydroxy groups is 20% to 30%;
the median particle size d 50 of the primary particles of the microgel is 40 to 80 nm;
the microgel comprises at least about 90% by weight of fractions insoluble in toluene at 23° C.;
the swelling index of the microgel in toluene at 23° C. is 1 to 15;
the glass transition temperature of the microgel is from −40° C. to −15° C.;
the breadth of the glass transition range of the microgel is greater than about 20° C.; and
the thermoplastic/microgel ratio is 97:3 to 85:15.
15. A thermoplastic composition comprising:
polyvinyl chloride, and
hydroxy-functionalized, polybutadiene-acrylonitrile copolymer microgel, crosslinked with organic peroxides.
16. The thermoplastic composition according to claim 15 , wherein the microgel has a hydroxy number of 0.1 to 100 mg KOH/g of polymer as determined in accordance with DIN 53240 via reaction with acetic anhydride and use of KOH for titration of the acetic acid liberated.
17. The thermoplastic composition according to claim 16 , wherein the hydroxy number is 0.5 to 50 mg KOH/g of polymer.