DE1620870C - Process for the production of elastic moldings - Google Patents

Description

3 4

is in the USA patents 2,820,773, 2,820,809 glycol dimethacrylate, 1,3-butanediol dimethacrylate, tri-

and 3 238 275 as well as in the British patent ethylene glycol dimethacrylate, tetraethylene glycol

841 889. methacrylate and trimethylolpropane trimethacrylate.

By using mixtures of graft The amount of in the molded polymer according to the invention co-hardening monomeric ester present with other thermoplastic compounds The properties of the rubber is preferably 1 to 25 parts by weight per materials change. This can be done in a manner known per se, 100 parts of cis-1,4-polybutadiene. But it should be noted. B. as in U.S. Patent 2,820,773 that the use of more than 25 parts wrote, by mixing additional acrylic monomeric ester in general to extremely hard ones nitrile-styrene copolymer latex with the latex of molded objects with less good back-grafted properties Material and joint failure resilience and therefore less useful than reach. This technique enables the manufacture of golf ball leads.

of shaped objects with largely under- Examples of free usable according to the invention

different properties, e.g. B. golf balls, which are free radical polymerization initiators

either for golf target practice or extensive 15 organic peroxides, such as lauroyl peroxide, benzoyl

Balls are suitable. The proportions of the so peroxide and t-butyl hydroperoxide and other, free

mixed latex types are set so that radical-forming compounds such as azobisiso-

that the resulting graft copolymer is at least butyronitrile.

5 percent by weight and up to 60 percent by weight are preferably used as free radical poly rubber. 20 merization initiator dicumyl peroxide, e.g. B. a han-

It is preferable to use a total of 30 to the usual dicumyl peroxide on calcium carbonate

70 parts by weight of fillers per 100 parts of cis-l, 4-poly-carrier, which is composed of 40 ° / ₀ peroxide and 60 ° / ₀ CAI

butadiene. The amount of calcium carbonate in the molding compound.

brought fillers depends on the amount of the other The amount of initiator in the invention ■

Components, as well as the desired properties 25 to be vulcanized molding compound is expedient-

of the molded object. If, for example, 1 to 5 parts by weight per 100 parts of cis-

wise the amount of all other constituents of the 1,4-polybutadiene.

Mixing constant, this increases the compressive strength - molding compounds are preferably vulcanized,

speed of the ball (a measure of the hardness) with the content per 100 parts by weight of cis-1,4-polybutadiene, 15 to

of fillers, whereas the rebound resilience and 30 50 parts by weight of graft copolymer, 30 to 70 parts

the resistance to cuts parts by weight filler, 1 to 25 parts by weight mono-

to take. contains mere ester and 1 to 5 parts by weight of initiator.

10 to 30 parts are preferably used. Mixing is carried out below using the Her titanium dioxide per 100 parts of cis-1,4-polybutadiene. The position of golf balls explained. Of course Properties of the shaped object and, in particular, many other objects with large special golf balls' are manufactured in an analogous way to impact strength. Fluctuations in the content of this filler not in the manufacture of golf balls under Verwenallzu sensitive, since this is mainly a white manure of the molding composition according to the invention Pigment and serves as a weight control agent. individual components are uniformly combined

The polyfunctional used, as a cohardening 4 ° mixes, and the resulting mixture then becomes an agent serving monomeric ester, which the permanent adhesion of the molded article and its vulcanized under heating and application of pressure. In general, all ingredients, greater compressive strength, consists of one, with the exception of the monomeric ester and the polyunsaturated ester, of an alcohol and an itiators, on a conventional two-roll chewing of a carboxylic acid, only one of which is more than 45 chukmühle or in a Banbury mixer an ester-forming functional group may have a temperature of 121 to 149 ° C mixed. The unsaturation can be either in the acid, the resulting uniform mixture is allowed to, or in the alcohol or in the two compounds then forward to cool to below 51 ⁰ C and then the lie. Thus, saturated polyols (diols, triols acting as co-hardening monomeric esters, etc.) may only be esterified with unsaturated monocarboxylic acids to 50 and the initiator on a cold two-roll polyunsaturated ester, since rubber mill or in a cold banbury the polyols more than one ester-forming functional mixer, preferably at temperatures not over group. Such esters can be at -51 ° C to prevent premature conversion of the ester, for example, from polyhydric alcohols such as ethylene and the initiator. The resulting glycol, diethylene glycol, 1,3-butanediol, neopentylene mixture is then formed into pellets, which glycol, triethylene glycol, tetraethylene glycol, glycine can be cylindrical or spherical and a rin, trimethylolpropane, pentaerythritol or sorbitol slightly larger in volume than that the mold with unsaturated monocarboxylic acids such as acrylic acid. These compacts or preforms will then manufacture methacrylic acid, or other alkene carboxylic acids into the golf ball molds with a conventional one. The alkene carboxylic acids can also be converted with a diameter of 4.26 cm, which veralkohol or methallyl alcohol with monoolefinically unsaturated alcohols, such as allyl projections for producing depressions, can be seen according to the invention; In these, the molding then takes place in the case of useful esters, such as allyl methacrylate esterified at high pressure and elevated temperature, with the. The alkenols can also be vulcanized with saturated bricks. Preferably, olefinic polycarboxylic acids, such as amber 65 vulcanizing in the form of misacid, maleic acid or fumaric acid will be esterified. grooves at 177 ° C and a piston pressure of

The monomeric ester used is, for example, 211 kg / cm ^a . The resulting balls

Polymethacrylic acid esters of glycols such as ethylene are cooled in the mold to room temperature

and then removed. Then the ridges present at the equator of the balls are cut by cutting and buffing away. The balls are then ready for use.

B ei s ρ i el e

The following exemplary embodiments are compiled in tabular form for the sake of clarity serve to further explain the invention. All parts are based on weight. The example 7, in which no graft copolymer was used, is only used for comparison purposes and represents does not represent an embodiment of the invention. The measurement of the compressive strength was carried out in a so-called Professional Golfers' Association (PGA) meter.

1 2 3 4th 5 6th 100 100 100 100 100 100 20 ^d > 301) 40 ^d > 30 ^e > 40 ^e > 40 « 20th 20th 20th 20th 20th 20th 40 40 40 40 40 40 10 10 10 10 10 10 10 10 10 10 10 10 49 62 72 62 69 49 73 71 67 71 69 69 115 130 135 135 135 140

7 *)

Components
cis-polybutadiene ^a >
Graft copolymer
Styrene-acrylonitrile resin ^b )

; precipitated hydrated calcium silicate

Ethylene dimethacrylate

40 ° / ₀ dicumyl peroxide + 60 ° / ₀ calcium carbonate .. Properties

Compressive strength, PGA ^C >

Rebound resilience, ° / ₀

Resistance to cuts (relative) 100

40
20th
40
10
10

77
70
95

*) This example is not an example according to the invention, but merely serves for comparison.

a) 96 ° / _o cis-1,4 content.

b) Copolymer of 72% styrene and 28% acrylonitrile.

c) This value varies according to the hardness.

d) reaction product of 50 parts by weight of polybutadiene. 34 parts of styrene and 16 parts of acrylonitrile mixed with additional ■ Acrylonitrile-styrene resin. (b); -

7 ° / ₀ of the total weight of the resin consisted of Keutschuk.

e) reaction product of 50 parts by weight of polybutadiene, 34 parts of styrene and 16 parts of acrylonitrile, mixed with additional Acrylonitrile-styrene resin (b);

26% of the total weight of the resin was rubber.

f) reaction product of 50 parts by weight of polybutadiene, 34 parts of styrene and 60 parts of acrylonitrile; 50% of the total weight of the resin was rubber.

The examples are now explained in more detail below. The physical properties of the invention The balls produced are summarized in Examples 1 and 6.

The influence of the different resin content with the same percentage of rubber at the same time in the graft copolymer results from the balls according to Examples 1, 2 and 3. Increased the amount of graft copolymer increases the PGA compressive strength and the relative resistance compared to cuts, although the rebound elasticity is somewhat reduced. Man however, observed no significant change in relative resistance to cuts when 30 or more parts of graft copolymer are used.

The rubber content in the graft copolymer is increased from 7 to 50%, balls with lower compressive strength are obtained, as can be seen from the Examples 3, 5 and 6 give without, however, the rebound resilience and the relative durability compared to cuts would be significantly affected. Example 7 shows the importance of the graft copolymer on the properties of the golf ball. In this example, there was 40 parts of a styrene-acrylonitrile resin used. Comparing the results obtained in this example with the examples 3, 5 and 6, it follows that if the graft copolymer is omitted, which changing Contains amounts of grafted rubber, a ball with greater compressive strength, but substantial less resistance to cuts. The percent resilience was also a little bit higher.

Claims (2)

1 2 of a compact, unitary golf ball, claims result: there are special advantages in that the many process stages in the manufacture of a 1. Process for the production of elastic molded yarns with an existing core are eliminated. The moldings by vulcanizing homogeneous molding compounds, you can also use them to produce the external compounds on the basis of graft copolymers layer a golf ball with conventional core made of polybutadiene or butadiene-styrene-copoly- wound yarns is used merisaten with a salary of not over will be. In general, the molding compound is for manufacturing 10 weight percent styrene and many other grafted items with great rebound styrene and acrylonitrile, optionally in a mixture suitable for elasticity. with a copolymer of acrylonitrile and The molding compound preferably contains as the mainstyrene, fillers and a polyfunctional component cis-1,4-polybutadiene with at least one of the monomeric esters serving as co-curing agents 85 ° / ₀ and preferably 95 ^ό / ₀ cis-1, 4 configuration. with at least two non-conjugated double The proportions of the other constituents of the mold bonds, characterized in that 15 masses are usually in parts by weight, based on a homogeneous mixture of cis-1,4-poly per 100 parts by weight of cis-1,4-polybutadiene, angeutadiene and the graft copolymer in counterpart. By using cis-1,4-polybutadiene, a polymer which forms free radicals as the main polymer component in the molding compound, the sationinitiator is at a temperature above that, the desired, very good rebound activation temperature of the initiator is obtained in all as elastic properties. The other ingredients, heated in a known manner. namely the graft copolymer, the filler, the 2. Use of the molding compounds according to anomeric esters and free radicals Claim 1, for the production of golf balls. Polymerization initiator are added to the mass, around the compressive strength properties as speaking. The resulting formed The object has, in particular in the case of a golf ball, preferably a rebound resilience of The object of the invention is to produce approximately 70% elastic. Moldings with good rebound elasticity and The graft copolymer consists of a basic compressive strength properties. The polymer used according to the invention made of polybutadiene or a butadiene Molding compounds are particularly suitable for styrene rubber with a content of no more Manufacture of golf balls. than 10 percent by weight copolymerized styrene, The invention relates to a process for the production of elastic moldings by vulcanization onto which styrene and acrylonitrile have been grafted; furthermore, this is to be understood as meaning a mixture of homogeneous molding compositions based on such a graft copolymer with a Covon graft copolymer made of polybutadiene or polymer made of styrene and acrylonitrile. Butadiene-styrene copolymers with a content The graft copolymer preferably does not contain more than 10 percent by weight of styrene and more than 60 percent by weight of butadiene- or butane-grafted styrene and acrylonitrile, optionally a diene-styrene base polymer and the amount of mixed with a copolymer Acrylonitrile is 40 styrene and acrylonitrile units, respectively, and styrene, fillers and a polyfunctional, at least 40 percent by weight of the graft copolymer serving as a co-curing agent monomeric ester. Regardless of whether the graft copolymer with at least two non-conjugated double bonds is made from a mixture with another thermodung, characterized in that it is a homoplastic resin or not, the mixture of cis-1,4-polybutadiene and the 45 amount of des Rubber base polymer, preferably graft copolymer in the presence of a free radical, always 5 to 6 percent by weight of the total polymerization initiator in relation to a temperature of the graft copolymer.
temperature above the activation temperature of the initiator The graft copolyin used in the molding composition is heated in a manner known per se. merisat has a notched impact strength at -40 ⁰ C. By changing the proportions of the one 50 of over 1.383 · 10 * g · cm per cm of an Izod notch Individual components of the molding compound can be used (ASTM test D 256-84T). Change the balance of properties in the resulting molded article. Thus, acrylonitrile copolymer contains about 70 weight, for example, the hardness at the expense of the reverse percent styrene and about 30 weight percent acrylic resilience increase slightly by adding 55 nitrile. The relative amounts of these two monodes increased content of graft copolymer and the mers can be reduced between 60 to 90 percent by weight of cis-1,4-polybutadiene. Generally styrene and correspondingly 40 to 10 percent by weight of the graft copolymer will be in the acrylonitrile molding compound. In general, styrene is used to increase the compressive strength of the molded component and acrylonitrile as a minor component.
To increase the object without affecting the rebound elasticity too much. Furthermore, the graft copolymers used can take into account that an excess of monomeric known manner results in a polyhard object for some purposes by copolymerization of styrene esters and acrylonitrile monomers in the latex. Other slight butadienes or a copolymer of butadiene, variations in the properties can be obtained by 65 and styrene, this copoly change in the relative proportions of the merisate not achieving more than a total of 10 percent by weight of constituents of the molding compounds. Styrene based on the total weight of butadiene If the molding compound is used for manufacturing and contains styrene. The manufacture of these resins