FI57772B - SAETT ATT FRAMSTAELLA MJUKGJORDA ELLER STYVA POLYVINYLCHLORIDEPRODUKTER AV SUSPENSIONSPOLYMERISERAD VINYLKLORID - Google Patents

Description

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Patent Meddelat v (S1) Kv.ik.Wci.3 C 08 L 27/06 FINLAND — FINLAND (21) PtMnttlhtkxnm - Pmnttm6kn> n | 3716/72 (22) hUk «miipl) v (- Ana6knlngadt (29.12.72 (23) Alk» HM ~ GlW * h «» d «* 29.12.72 (41) Tullut JulkMal - Kllvlt offuntllg ΐδ. 08 73 f- l * r * ltt «1haint« (44) HKMIW »I.

nMant · odi registwrstyrdMit '' AmMcm uttagd eeh utUkrMtan publicurad 30.06.80 (32) (33) (31) PH »* · # Y utuellwiit — luflrd prtorttut lJ. 02.72

Sweden-Sweden (SE) 19 ^ 2/72 (71) Bergviks Hartsprodukter Aktiebolag, 820 22 Sandarne, Sweden-Sweden (SE) (72) Ragnar Ivemark, Sandarne, Erik Mariedahl, Sandarne, Sweden-Sweden (SE) (lb) Berggren Oy Ab (5 * 0 Method for the manufacture of softened or rigid polyvinyl chloride products from suspension polymerised vinyl chloride - Sätt att framställa mjukgjorda eller styva polyvinylkloridprodukter av suspensionspolymerise-rad vinylklorid

Polyvinyl chloride is today one of the most important basic materials for thermoplastics in terms of quantity. emulsion PVC prepared by emulsifying vinyl chloride emulsified in water to give a relatively fine-grained polymer having good plasticizer absorption and water absorption. A better and currently widely used polynerization method gives the so-called suspension PVC, which is characterized by coarse granularity, low moisture absorption, good absorption of thinning agents but poorer gelling properties. The latter polyvinyl chloride. is currently considered to be more advantageous than the arrow of its mechanical and thermal properties in numerous applications.

However, in the manufacture of suspension-based PVC-based products, it has proved difficult to clot the plastic material in a short time and with normal handling, so that subsequent molding produces goods with satisfactory homogeneity, appearance and breast properties. This difficulty occurs especially when the 57772 molding is performed solely by extrusion, and the sheets or foil are produced by calendering alone, but it also occurs in extrusion during calendering. Because these molding methods are the most economical in mass production. there has been a bladder trying to facilitate the shaping of the suspension PVC by using this plastic mixed with another substance even when this is at the expense of the properties of the final product. Thus, it is known to add to suspension PVC various products with a lower melting range than olyvinyl chloride, for example acrylic olymers, polyethylenes, etc. Alternatively, emulsion PVC can be mixed into the suspension PVC, or special co-monomers of vinyl chloride and other vinyl monomers can be prepared. . However, the latter method, which is relatively expensive, is probably the most common in the manufacture of rigid products based on susoen-sio-pVC. As such a product has a large and growing market in the manufacture of various profiles, pipes and building elements, the difficulty of using ordinary suspension pVC for these purposes has slowed down development.

The most common way to reduce the difficulty in shaping suspension PVC is to add diluents. However, it is known that the addition of common plasticizers, e.g. diethylhexyl phthalate, adversely affects the properties of the product in many respects. The softened substance receives e.g. The tendency of ordinary softeners is also characterized by the fact that while the elongation at break is increased, the tensile strength decreases considerably, which of course is not the intention. The substance should preferably retain its toughness and tendency, although it should To achieve this goal, it is common to limit the addition of plasticizer to the minimum amount necessary for actual softening, and thus there is a great need for softened products to facilitate modification other than by using larger softeners *.

According to the invention, it has now surprisingly been found that it is possible both to facilitate shaping and to substantially improve the properties of the finished product in the production of softened or rigid nolyvinyl chloride products from suspension-polymerized vinyl chloride, preferably in products molded by extrusion and / or calendering. It is characteristic of the process that a powdery resin-modified alkyd made of a resin material containing more than 95% by weight is added to and mixed with rolyvinyl chloride in powder form before or during molding. free resin acids (so-called oil-free stills) and having a dilution density of at least 90 ° C as measured by the bead ring method. The alkyd is then added in an amount of up to 10 parts by weight per 100 parts by weight of nolyvinyl chloride. Said softening point, at least 90 ° C, distinguishes the high resin oxygen alkyds used according to the invention from all lower resins on the market, which have a lower resin content and instead contain fatty acids or other by-products. Preferably, an alkyd is used which is made from rosin taps obtained from tall oil and which is enriched relatively well with oxidation-resistant rosin acid isomers.

The advantages of the new method are particularly obvious when the product is formed by extrusion or calendering, since in this case there is no need to compromise on the properties of the final product, as has been the case with known modification facilitation measures.

An essential advantage of the invention is that the quality can be improved even if a cheaper raw material is used. The strength of the product is in many cases comparable to the strength of products made from much more expensive polymers such as, for example, ethylene vinyl acetate-modified vinyl chloride (oxazolymers), chlorinated nolyolefins added polyvinyl chloride, etc. A significant improvement in mechanical strength is achieved through a simultaneous increase in tensile strength and elongation at break. The known and normal relationship between these two properties is that as the value of one increases, the value of the other decreases. The volatility of the fermenter is also reduced due to the fact that the oil-free, resin-modified alkyd can be combined with both the plasticizer and the polymer very well. For the same reason, water absorption also decreases. Products made according to the invention by extrusion have a substantially better appearance and better homogeneity due to the rheolope-modifying effect of the alkyd, which manifests itself in an increase in the melting rate and a decrease in the internal friction of the substance during melting. This results in a smoother and more homopenic material flow during the molding step. Due to the good thermal stability of the alkyd, the thermal stability of the polyvinyl chloride product according to the invention does not deteriorate.

Alkyds are known to be in principle olipomers, i.e. polymers consisting of an olesterester chain with a range of di-57772 carboxylic acid units and polyol units (usually 3- or * 4-value alcohols), the free hydroxyl groups of the chain being utilized with carboxylic acids to modify the alkyd so that the # alkyd acquires the desired physical and chemical properties. Because the composition and length of the nolyester chain and the nature of the side chains can vary quite widely, the possibilities for combination are virtually limitless. The best known is an alkyd commonly used as a binder in dyes and varnishes, in which the modifying side group is a saturated moiety, or a saturated fatty acid having about 13 carbon atoms. Alkyds that are not modified with fatty acids are commonly referred to as "oil-free". The term "resin-modified alkyd" does not refer to typical fatty acid-modified alkyds, but instead to "non-fatty" alkyds modified by esterification with resin acids which are the main constituents in a natural resin obtained from various sources, for example colophon or pine. , in disproportionated or dehydrated forms of the correspondingly hydrogenated natural resin, respectively. What these resin materials have in common is that the content of free resin acids in them generally does not exceed 80-90% by weight and never exceeds 95% by weight, which adversely affects the composition of the alkyds prepared therefrom. The softening point of these alkyds is always lower than 90 ° C, usually 70-80 ° C.

The invention is explained in more detail below in connection with application examples ·

Example 1

Softened pVC mixtures were prepared as follows: Λ. Basic recipe (Comparison) S-PVC, K-value 70-72 100 parts by weight DOP (diethylhexyl phthalate) ** 5 "DOS (dioctyl sebacate) 10

Ba / Cd stabilizer 0.9 "chelator 0.3" lubricant 0.6 "3. Various compositions of the invention were prepared by adding to the basic recipe an oil-free resin-modified alkyd having a softening point of 107 ° C, reducing the DOP content, as follows:

1) DOP M parts by weight / 100 parts S-pVC

alkyd 1

2) DOP ^ 3 parts / 100 parts S-PVC

alkyd 2

3) DOP l \ 2 naino parts / 100 parts S-pVC

alkyd 3 "" 5 57772

The mixing was performed by mixing the liquid additions - oehmenr.in, chelator and lubricant - together, after which the resin alkyd was dispersed in a liquid mixture, which was then mixed with a thoroughly mixed PVC powdered Ba / Cd stabilizer mixture with thorough stirring.

The powder mixture was prepared on a two-roll roller with a roll surface temperature of 85-90 ° C, and the roll speed was selected to be 9 and resp. 11 rpm The speed difference was necessary to bring friction to the roll nip as the pulp passed through it. The roll clearance was about 0.5-1 mm. In this way, the polymer quickly absorbed the plasticizer and additives, forming a powder mixture that was extremely flowable. The good flowability required for direct extrusion was achieved when the composition contained an oil-free resin-modified alkyd.

In an extrusion apparatus equipped with a single-threaded feed screw and a nozzle consisting of an outer part of 19 mm in diameter (matrix) and an inner part of 17 mm in diameter (spindle), a hose with dimensions of 15 mm / 15 = was made by conventional extrusion techniques. from the above mixture. The appearance of the hose was visually evaluated for surface structure and homogeneity. Because the hose was transparent, it was possible to observe the flow conditions during processing. The appearance was rated on a scale of 1 to 5, where 1 is a flawless hose with no surface defects or visible obscurances, and 5 is a hose with very visible surface defects and run defects.

The tensile strength and elongation at break as well as the tear strength in the transverse direction were determined from the manufactured hose.

Thermal stability, plasticizer volatility, and water absorption were determined from both the control sample and the sample of the invention by rolling 0.7 mm thick films with a two-roll vsls material at a speed of 22 rpm at a surface temperature. 160 ° C. During the rolling process, in which the starting material was only mechanically mixed starting material, the gelling rate and general behavior of the various mixtures were studied.

Thermal stability was determined electrophotometrically from membrane samples treated at 178 ° C for 10, 20, 50, 50 and 60 minutes. The final evaluation was performed according to a scale of 1, where 1 means no or negligible deterioration and severe color deterioration.

r 57772

Outer Soft ~ Water Heat Shape ^ Tensile Fracture- Tear-Off Qbsorp- Stability- (Strength of Stretch # Strength of Evaporation Ti (Scale 1-5) (kp / cm1-) (?) (Kp / mm ) (?) (?) ko 1-4) ARef 11 165 550 6.2 0.70 0.06 1 3D 2 175 570 6.5 0.50 0.05 1 2 135 560 6.5 0.40 0.05 1 1,190,530 7.1 0.45 0.04 2

As can be seen from the table, a product with a substantially narrower appearance was obtained when the recipe contained a resin-modified alkyd, compared to the corresponding mixture to which this alkydine was not added. Mvds shows that the toughness of the product was higher than its tensile strength - higher tear strength and elongation at break - and that its resistance to deforming load was higher - the tensile strength increased. In addition, the volatility of the plasticizer decreased due to the very good compatibility between the polymer and the plasticizer and the correspondingly resin-modified alkyd of '61. This appearance improved the aging resistance - stiffening due to evaporation of the fermenter. The absorption of water by my nose also, which would nibble on numbness in the cold. In addition, the shaping of the pulp was facilitated both by calendering (shortened the gel time) and by extrusion (increased production capacity and nasal smoothness) when said alkyd type is not mixed with susoensio pVC. Thermal stability did not deteriorate.

Example 2

Semi-rigid pVC mixtures were prepared as follows: A. Basic present (comparison) S-PVC, K-value 70-72 100 ^ Aino-part DOP 20 ”

Ba / Cd Stabilizer 1.2 "Chelator 0.4" Lubricant 0.8 "n. Various compositions of the invention were prepared for nerve resin by adding a clear, resin-modified alkyd having a softening point of 107 ° C and reducing the DOP content as follows: 1) DOP 19.5 r »Single alkyd 0.5 2) DOP 19" alkyd 1 "3) DOP 17 alkyd 5"

The mixing and preparation of the powder were carried out in the same manner as in Example 1, except that the temperature in the preparation of the powder was 105 ° C.

7 57772

In the same extrusion device as in Example 1, but using a nozzle with a 16 mm diameter outer part (matrix) and an 11.5 mm diameter inner part (spindle), a tube with dimensions du / ds = 15/11 was prepared. The appearance of the tube was visually evaluated by the surface structure and homogeneity arrow. Due to the transparency of the material, it was possible to determine the flow conditions during processing, taking into account any flow errors that may occur in the article. The appearance was evaluated using the same scale as in Example 1.

To determine mechanical strength (tensile strength and elongation at break) as well as water absorption and thermal stability, a 0.7 mm thick film was rolled from each sample in a two-roll rolling mill at 22 rpm and 165 ° C. During the rolling delivery, in which the starting material was mechanically mixed components, the gelling complexity and general behavior of the various alloys were studied.

Thermal stability was determined and evaluated as in Example 1.

Appearance Tensile- Fracture- V ° den ab- Lämröstab? - (scale strength, elongation sorption lithium (as-1-5) (kp / cm; (¾) (?) Theorem 1-¾) ARef 3 380 280 0.08 1 -τ) 2 390 310 0.07 1 3 2 l »10 320 0.07 1 r) 1 420 3 * 40 0, 06 2

As can be seen from the table, extrusion yielded a significantly better product when the recipe contained an oil-free resin-modified alkyd, compared to the corresponding mixture without the presence of this type of alkyd. The rolled film obtained better mechanical strength and lower water absorption, without deteriorating thermal stability. In addition, shaping was facilitated both during calendering (gelation time was shortened) and extrusion (increased production capacity and surface smoothness). Likewise, the preparation of a free-flowing, extrudable powder mixture was facilitated when this alkyd naphtha was included in the composition.

Example 3 Rigid PVC blends were prepared as follows.

A. Basic recipe (comparison) S-PVC, X value 64-66 100 parts by weight

Dibutyltin stabilizer 3 "

As a lubricant Ca-stearate 0.5 ”wax (flowable) 0.8" 8 57772 3. Various mixtures according to the invention were prepared by adding to the basic recipe an oil-free resin-modified alkyd with a softening point of 102 ° C as follows: alkyd 1.0 3) alkyd 3.0

The mixing was carried out by thoroughly mixing the dry, powdered components S-PVC, Ca stearate and the oil-free, resin-modified alkyd, after which the liquid stabilizer and the mixed liquid lubricant were mixed thoroughly with stirring. The extrudable powder mixture was prepared as described in Example 1, except that the surface temperature of the rolls was 110-115 ° C.

In the extrusion apparatus, using the same die as in Example 1, a tube with dimensions du / ds = .17 / 15 was prepared by a conventional extrusion technique. · The appearance of the tube was visually evaluated for surface structure and homogeneity. Due to the transparency of the material, it was possible to determine the flow conditions during processing by taking into account any flow defects that may occur in the article. The appearance was evaluated according to the same scale as in Example 1.

To determine the mechanical strength (tensile strength and elongation at break) as well as the water absorption and thermal stability, a 0.7 mm thick film was rolled on a two-spindle roller at 22 rpm with a surface temperature of 177 ° C in each sample. During the rolling supply, in which the starting material consisted of a mechanically mixed component, the gelling rate and general behavior of the various alloys were studied.

Thermal stability was determined and evaluated as in Example 1.

Appearance Tensile- Fracture- Water ab- Thermo- stable- (scale strength elongation sorption teet (as- 1-5) (kp / cm2) (%) (3) teikk 1- ^) ARef 3,500 15 0.10 1 Β ±) 3,520 15 0,09 1 32) 2 530 17 0,09 1 1 560 25 0,08 1

As can be seen from the table, extrusion gave a better appearance product when the reseot contained an oil-free, resin-modified alkyd, compared to the corresponding mixture in which this

Claims (4)

9,57772 alkyds were not included. The rolled film received substantially better mechanical strength and lower water absorption, without compromising thermal stability. In addition, the processing was facilitated both by calendering (shortening of the gelling time) and by extrusion (increased production capacity and improved surface smoothness). Likewise, the preparation of a free-flowing, extrudable powder mixture was facilitated when said alkyd type was included in the composition. Although the effect of the object of the invention can be observed even with very small alkyd additions, a more obvious result is achieved only when the addition is at least 0.5 parts by weight of alkyd per 100 parts by weight of polyvinyl chloride. 1. A process for the preparation of softened or rigid polyvinyl chloride products from suspension polymerized vinyl chloride, preferably by extrusion and / or calendering of molded articles, characterized in that powdered polyvinyl chloride containing more than 95 weight? free of rosin acid (of the so-called oil-free type) and having a softening point of at least 90 ° C as measured by the ball-ring method, with the alkyd being added in an amount of not more than 10 parts by weight per 100 parts by weight of polyvinyl chloride. Process for the preparation of rigid polyvinyl chloride products according to Claim 1, characterized in that 0.5 to 5 parts by weight of an oil-free, resin-modified alkyd per 100 parts by weight of polyvinyl chloride are added to and mixed with polyvinyl chloride without any plasticizer, before or during shaping and molding. . A process for preparing semi-rigid polyvinyl chloride products according to claim 1, wherein up to 20 parts by weight of a plasticizer of a known type per 100 parts by weight of polyvinyl chloride are mixed with the polyvinyl chloride, characterized in that an oil-free, resin-modified parts by weight per 100 parts by weight of polyvinyl chloride. The method of making soft polyvinyl chloride products according to claim 1, wherein up to about 60 parts by weight of a plasticizer of a known type per 100 parts by weight of polyvinyl chloride are mixed with the polyvinyl chloride, sensation t, Axp. s i i-