IL27431A - Halogenation of vinyl polymers - Google Patents

Description

relates to of vinyl particular to vinyl of vinyl dissolved in organic liquids capable of polyvinyl chloride highly having a towards solvents starting polymeric materials reaction temperatures to of stability able of resistant of processes the of fee polymeric the liquid in which o the properties of copolymers of vinyl such for the of a d a good of the operties at high She degree of m the process Sons processes propose tut t vinyl chloride by suspension of the in an which only very swelling of the The may be constituted by a or a s and processes the latter type o highly chlorinated polymeric materials are particularly suited for the preparation goods with hi h thermal however such a the of to recovered at fee e of the is It of fee to provide a process for the ehlorination of vinyl chloride polyneric materials is relatively simple and which has or drawbacks disadvantages than the known According this there of in a vinyl or minor quantity of a at the ehlorination reaction is is not it is however preferred to operate at temperatures below the glass transition temperature of the and a preferred temperature range is from to vinyl as h a and as as to pol and and copolymers of vinyl chloride In the case of polyvinyl chloride it preferred to a obtained by aqueous a defined by its viscosity in a solution of the in parts by weight parts by of sal else to according to S δ 140 mesh 40 200 20 Such polymers have a percentage of combined of of about glass transition temperature of of 75 kg 1 of about 85 to a porosity expressed as the the of to a diameter of the of from to can be effected processes for It is preferred o dry may be activated either by physical chemical In it is to operate in the presence of active l ainc s or the capable of the free for with decomposition halving the the to this such as c be y the quantity tine is a obtain1 a with the ereentage of chlorine a wide range of suitable ly a r tetrachloride and its wide quantity of by or is factor in the it allows to o having desired pro of on c material that on its on mil as the us If reaction is slow and a chlorinated product with poor stability iis if tile of the too the chlorinated or such a to be forced on walls of the reaction it is to material powdery la to the invention the c it that the best are by per weight of to preferably from to by The mixture of polymer and chloroalkane achieved by absorbing the chloroalkane in the preferably at room It is to w ork with equipment similar to that normally used in the preparation of mixtures of polyvinyl chloride and In the process of the it is to operate in total absence of the presence of very small quantities of either in the material or in can be Bes results are obtained when the total quantity of water present is less than by The chlorinated polymers o copolymers of the vinyl chloride obtained according to the invention have a better thermal stability than that the startin polymer or The term is defined herein by the following two according to the the quantity of HGl evolved at in a nitroge current 1 g of polymer is determined for a time of at leas Thereupo the slope of the graph of the quantit of HC1 as a function of the heating time The expressed in and called as is the stability of the polymer improved the time necessary for the appearance colour as well as the time required for this colour to turn in a sample of powdery kept aluminum crucibles in an oven with air circulation at a temperature of is When chlorine is introduced into a vinyl chloride polymer The polymeric powder thus is then treated with an aqueous solutio of to eliminate the last traces of the polymer obtained washed wit a solvent such as in to remove the last traces of the After solvent has been the average particle dimensions of the chlorinated polymer as well as the distribution of the granulometry of the particles resume substantially the same values as the starting The chlorinated polymers and copolymers may be processed on machines and equipment usually used in the processing of the polymers and For to produce a rigid vinyl sheet through a a temperature range of from 180 to can be used as the most suitable temperature range for processing a chlorinated polyvinyl chloride containing from to by weight of The chlorinated polymers prepared by the invention ma be plasticised in the same manner as the starting vinyl polymers and even if the normal plasticisers are less effective with the chlorinated polymers than with the starting Moulding compositions based on chlorinated polymeric materials obtained according to the may obtained b mixing the materials with the conventional additives such as lubricating and detaching agents which are with polyvinyl The invention is illustrated by the following in which mesh sizes are those of the Official United States and Tg denotes the glass transition of Properties Unohlorlnaed aft three hour Porosity of particles of diameter of Particle by a 40 0 0 mesh 0 0 80 0 0 0 1 0 41 52 200 40 55 200 12 Specific t Percentage chlorine 65 at technical stabilit after JO 60 after 100 140 81 penetration 87 Using the in Example awl of polyvinyl with different ratioe of polyvinyl Different times required to obtain dry powdery mixtures of the polymer and reaction conditione are in Stable below TABLE i 548 200 200 200 Time for obtaining a dry powdery 50 70 Chlorlnation 4 4 4 4 Chlorination temperature 26 The properties of the chlorinated are out in Table The results obtained show that an inereaee of quantity of ae the remaining the considerably increases the consequently the quantity of chemically combined and thus gives products with better resistance to and of better thermal In this Example a reaction apparatus similar to of Example 1 was except that the flask had a ca 20 litres and was rotated at revolutions per tests were made at different conditione and different In a first test mixed with 400 cc o three after which the powdery Mixture reached the The was then effected the presence of a mercury ultraviolet chlorlnation reaction was carried out over a period at a mean temperature of A second test F was carried out under the ditions except that the chlorlnation reaction tiae was six The results obtained in both tests are in The reaction as in 1 and the reaction conditions were the same except that instead of photochemical was by β Various tests were carried out under different conditions with different peroxide catalysts and at In a first test 300 g of powdery used and 0 cc of which contained g of Thereupon the two components were stirred for 85 minutes at 0 after which time a powder was The chlorlnation reaction in the same way as previously described a ter four hours of reaction at a product was obtained the properties of are recorded in Table dissolved 0 After four hours of reaction at 36 a chlorinated polymer was the properties of which are in Table III B a 1 Test A B e Specific 1 chlorine 59 6 Specific viscosity 0 88 93 101 131 1 Vicat penetration temperature 95 103 116 140 Thermal stability ma x x x x Technical thermal stability 15 30 40 70 5 80 100 110 140 Porosit i diameter 0 1000 g of Sicron vinyl acetate copolymer containing of chemically combined vinyl prepared by suspension and having the properties given in Table were i a litre apparatus by mixing first with 400 ml of treatment with dry gaseous chlorine at a temperature of 0 4 The reaction was promoted by irradiation with a 70 watt ressure mercury ultra violet The properties of the chlorinated product are set out in Table table From the abov can be seen that improved thermal stability and resistance to heat can be achieved by of a vinyl chloride vinyl acetate 7 Following the procedures described the Examples a copolymer of propylene vinyl about 4 of chemically combined propylene was starting from a mixture of 1200 g of the polymer and 400 o The reaction temperature was 20 the reaction time was 4 and activation was with ultra violet lamp as described in Example The properties of both the unchlorinated and chlorinated copolymer are set out in Table improvement in the thermal stability to heat are attained by chlorinat on of this vinyl propylene Specific at Specific weight chlorine Particle size percentage retained on a sieve 40 mean 0 60 mean 0 Θ0 1 100 mesh 2 140 mean 40 200 25 200 32 DHG eonstant Technical thermal after 25 after 78 penetration temperature insufficientOCRQuality

Claims (1)

r the chlorination of a chloride or the substantially anhydrous of a powdery mixture of the or copolymer with a minor quantity of a A process according to Claim 1 in which the is effected at a temperature below the glass transition temperature of the polymer or A process according to Claim 1 or 2 in which the chlorination effected at a temperature of from 0 to 4 A process according to any claims in which the chloroalkane is A process according to which from to preferably 40 to parte of are mixed with 100 parts by weight of the polymer or A process according to any of Claims 1 to 3 which the chloroalkane is cartoon tetrachloride or A process according to any of the preceding claims in which the chlorination is effected in the presence of a quantity of a peroxide type free radical A process according to Claim 7 which the catalyst ia or A process according to of Claims 1 to 6 which the chlorination is activated toy exposure to ultra violet A process according to any of the preceding Claims which water is present in an amount of less weight of the total weight of the powdery The chlorination a vinyl chloride polymer or copolymer accordance with

1. Claim 1 substantially as herein described with reference to A chlorinated vinyl polymer or when chlorinated by process as claimed in any preceding 1 Fibres films and other manufactured from a chlorinated vinyl chloride polymer or as claimed in Claim insufficientOCRQuality