DE1594218A1 - Adhesive mixtures - Google Patents

Description

PATENT LAWYERS 1534 218

DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH

COLOGNE 1, DEICHMANNHAUS

January 21, 1969 Fu / bz

Eo Io du Pont de Femours & Company, Wilmington 98, Delaware (V.St.A. ')

Adhesive mixtures

The invention "relates to adhesives, in particular so-called cements based on chloroprene polymers.

Adhesive solutions based on chloroprene polymers are generally sufficiently chemically stable, but many of these adhesive solutions tend to flocculate and to segregate during storage «This is troublesome as the cement reappears before use must be homogenized ο adhesive solutions Based on chloroprene polymers, magnesium oxide and contain a thermally reactive phenolic resin, such as those in the United States patent headed 2 610 910 are described, form adhesive bonds that have a relatively high level of cohesion at increased Temperatures, but these adhesive solutions tend segregation too quickly if left standing. It was also found to have certain uses than necessary, the chloroprene polymer by adding common accelerators or vulcanizing agents vulcanize to a crosslinked elastomer, however, these adhesives gel after the addition of the vulcanizing agent quickly, so that it is always necessary to un-

009834/1504

dfiUßlJntelJagerV. (Article 7älAbs.2Nr.1Satz3desÄnderuna8flea.v.4.9.1 »67}

BATH

mitterbar admix prior to use, which is inconvenient and expensive _o

The invention relates to an adhesive which contains the following components:

1) A solution of a chloroprene polymer in an organic solvent; here the polymer a) is a copolymer of chloroprene with a vinyl monomer which contains a carboxyl group and in which the CC double bond is activated by an adjacent carboxyl group, keto group or nitrile group, the copolymer 0.0 2-0.7 wt. - $ contains carboxyl groups, or b) a mixture of such a copolymer, which, however, up to 1 wt _o - $ contains carboxyl groups, with another chloroprene polymers, wherein said mixture 0.0 2 to 0.4 wt "- contains $ carboxyl groups;

2) an oil-soluble phenol-aldehyde resin in an amount from 10-100 parts by weight per 100 parts by weight of chloroprene polymer and

3) magnesium oxide, calcium oxide, Caloiumsulfid and / or lead oxide in an amount corresponding to at least 2 weight parts by _e magnesium oxide per 100 parts Chloroprenpolymeres β

Und.Vinylmpnomeren The copolymer of chloroprene is prepared by conventional methods, for "B ₀ of an emulsion of chloroprene and about 0.1 - z _o $ B contains ₀ methacrylic acid of the vinyl monomer, wherein the amount of - 5.0 wt" vinyl monomers the concentration of the carboxyl groups in the final copolymer determined · ₀ the preparation is carried out at 0 - 60 ⁰ C, preferably at about 40 ⁰ C, and to ensure adequate copolymerization of the less reactive vinyl

90983 /, / UCH

BAD ORfGINAL

; ■. ■ '■■. Ζ "'- 3 -.

preferably high monomeric monomers, for example Ms above about $ 70 and preferably Ms about $ 90, is worked. It is also possible that Polymerization to begin with an emulsion that contains the contains all vinyl monomers and only a part of the chloroprene, while the most of the chloroprene contains the System is added in the course of the polymerization. U.S. Patent 2,724,707 "describes the preparation of copolymers of dienes including

-10 "- · Chloroprene and vinyl monomers including acrylic acids.

The copolymer can be isolated by known methods, e.g. By removing unreacted chloroprene by steam stripping as described in U.S. Patent 2,467,769 and by freeze coagulation as described in U.S. Patent 2,187,146. Preferably, the _pH value of the latex is first adjusted to 8 or higher, such as in US Patent 411,729 planar beschri

Copolymers 0.0 2 - contained 0.7 i <> carboxyl groups, can be used for the preparation of the adhesives than those _·: be used, however, a carboxyl group content of 0.1 to 0.4 io preferred tilt decreases, carboxyl group content the adhesives segregate and do not show the same high adhesive strength at high temperature, while with increasing carboxyl group content they become more viscous and less easy to handle, until the polymers finally come to a carb

3q oxyl group content of more than about 0.7 ? * In the adhesive

are insoluble. Which are copolymers up to about 1 ^v $ Carb -.- '; contain ■■ oxylgruppen, can still be used if they are mixed with conventional chloroprene polymers, as mentioned above, these mixtures contain -

• 909834/1504

■ ■ - 4 -

preferably less than 0.2% / a carboxyl groups »The mixtures can be prepared by customary processes. be, ζ _β -Β «by Misohen of solid polymers on conventional Kautsohukmischwalzwerke or in Banbury mixers, mixing the Latioes and isolating the mixture, dissolving the polymers in a suitable solvent, together or separately with • subsequent mixing of the solutions, or also by mixing the adhesives "

The percentage of the carboxyl groups is to be calculated under the assumption that all the carboxyl groups in the copolymer in acid form are available "The determination can be made by known methods, _e Bo for by calculation on the basis of infrared analyzes ₀

• J5 Common adhesives based on chloroprene polymers often contain alkaline components, e.g. zinc oxide and magnesium oxide, around the chloroprene polymers to stabilize and slowly vulcanize applied mime at ambient temperatures, presumably

2Q lioh by reaction with allylic chlorine «, It becomes assumed that the divalent alkaline components in the adhesives according to the invention are one more more important role as a vulcanization or crosslinking agent play by forming ionic crosslinking bridges through salt formation with the carboxyl groups becomes magnesium oxide. The other alkaline constituents do not form adhesives that do not separate, the fast adhesive bonds of high. Strength at room temperature, but with adhesives,

3Q which contain calcium oxide and potassium sulfide, so far adhesives containing lead oxide that are not so strong at high temperatures, tend to get viscous after a woo or two,

90983A / 150A

however, "they form good bonds quickly and exhibit good bond strength at high temperatures." Preferably, about 4-10 parts of magnesium oxide per 100 parts of polymer are used. If another alkaline component or mixture is used, the desired amount in chemical equivalents is used Magnesiurnoxyd per 100 parts of polymer measured, the upper limit should preferably be 30 parts of magnesium oxide pJO not exceed "close These amounts of the alkaline components of 100 parts of polymer the unreacted already with the phenolic resin is a ₀

Phenolic resins are often blended in conventional adhesives based on Ghloroprenpolymeren to improve the durability of the tack, to lower the soheinbare viscosity or to improve the adhesion and cohesion ₀ The according to the invention erforderliohen öllösliohen phenol-aldehyde resins reduce the Heigung of the adhesive to Gelling

As oil-soluble phenol-aldehyde resins, the thermoplastic resins are suitable, which generally have moderately low molecular weights, are relatively little crosslinked and usually contain hydrocarbon substituents that give them oil solubility, Z ₀ Β »Purfurol-phenolic resins and phenol-modified coumarone-indene Resins, especially terpene-modified phenolic resins, such as can be produced, for example, duroh acidic condensation of terpene hydrocarbons or alcohols with phenol and subsequent catalytic resinification of the substituted phenol with formaldehyde. The resins are preferably used in amounts of 20-70 parts per 100 parts of the chloropreno-polymer. The use of the thermoplastic resins enables the production of adhesives which last for a period of 2-6 weeks

909834/1504

15S4218

does not gel, which is sufficient for many purposes » Without the addition of resins, gelation takes place in a few hours »adhesives that are thermoplastic Contain resins, retain their stickiness and stability against flocculation and segregation for a long time » The strengths at elevated temperatures are those of conventional cements based on chloroprene polymers, containing the same thermoplastic resins are superior.

However, thermally reactive phenolic resins _β are preferred. These can be prepared by adding about 1-2 moles of formaldehyde in the presence of an alkaline condensation catalyst with a phenol, including p-isopropyl, substituted in the p-position, for example with an alkyl radical with 3-8 carbon atoms -, p-Gyolohexyl-, pt-amyl and p-octylphenol, pt-butylphenol in particular, and are substituted with aryl phenol such as p-phenyl and tolylphenol implemented, _e These resins may be modified with the alkali material to form a see " Resin "are implemented, which only decomposes at very high temperatures of the order of 25O ⁰ O, but is nooh & Llöslioh. By using the modified resins in the adhesives according to the invention based on hloroprenoopolymers, adhesive bonds are obtained whose cohesion at high temperatures, ζ. »At 80-12O ⁰ O, about 3 - 10 times greater than the previously known adhesives based on chloroprene polymers containing these modified resins, quite apart from the improvement of the very serious segregation problem that occurs with the known adhesives of this type occurs "Adhesives according to the invention, which contain the modified phenolic resins, gel even after prolonged storage

909834/1504

not o adhesives that contain less than 10 parts of the modified resin per 100 parts of the polymer, have high viscosities immediately or shortly after manufacture, but adhesives have at least that Contains 10 parts of resin, initial viscosities in the same range as conventional cements based on chloroprene polymers, and the viscosity increases with the Time is not essential

The adhesives develop their adhesive strength - Relatively fast The adhesive strength is generally after 1 hour three ms ten times larger than conventional polychloroprene-based adhesives o one It is not intended to be bound by any particular theory however, it is believed that these rapidly obtained high bond strengths are from ionic crosslinking In contrast to crystallization in known adhesives, bridges arise.

All solvents are suitable for the production of the adhesives which are used for the production of the usual adhesive solutions and coatings based on orthoprene polymers. Mixtures of two or more organic solvents,-., of aromatic hydrocarbons such as toluene are preferred and xylene, aliphatic hydrocarbons, ketones, esters and chlorinated hydrocarbons, for "B _e, the following mixtures in which the numbers indicate the volume ratio: 1 ti: 1 Toluolt hexane: Äthylaoetat, 313: 3 * 1-toluene: hexane t ethyl acetate : Trichlorethylene, 3t 7-acetone heptane, 2: 8-toluene: ethyl acetate and 1: 1-toluene: hexane: methyl ethyl ketone.

Often other components that are used in conventional polychloroprene adhesives can be added

909634 / 15OA

become, ζ. Bo the following compounds (quantities are based on the chloroprene polymer) ι About 2 $ of a conventional antioxidant (preferably N-phenyl-naphthylamine if discoloration is not important, or an alkylated phenol if an antioxidant that does not form stains is required and no discoloration caused)} 2 to 10% zinc oxide, fillers such as clay, K _r eide, and carbon black, and pigments such as titanium dioxide, in particular in coatings, in which

• JO the deterioration of Kohäsionsfestig entering * · ness is not as wiohtig such as reducing costs or improving properties such as color, weather resistance and hardness _o curatives for common Polyohloropren adhesives are normally not required, but they may, in specific cases, for example, if maximum resistance to plastic flow is required, this may be advantageous ₀ For example, 2-meroapto-2-imidazoline, thiooarbanilide, combinations of lead oxide and aldehyde-aniline condensation products and 1,3,5-triethyl-s-triazine alone or in combination be used with lead oxide in amounts from 2-4 i °, wherein the lead oxide is an exception and is usually added in an amount of $ 20. About 2 - 4 fo contain sulfur in adhesives, the lead oxide and aldehyde-aniline condensation products, fast vulcanization result from tree temperature. Organic polyisocyanates, Z ₀ B ₀ 4 »4 ^I -diisocyanatodiphenylmethane, in quantities of 2 - 4 i <> cause vulcanization

30. sation at room temperature and result in increased bond strength in many applications. which elastomers must be glued with synthetic fibers »The vulcanizing agents are just like with conventional adhesives preferably added immediately before use ο

909834/1504

The adhesives can be prepared by customary methods, for example by kneading the chloroprene polymer with the components of the mixture, finally the resin on a mixing roller mill and dissolving the mixture obtained and the resin in a solvent in a cement mixer or other suitable mixer, but the Mastication must be kept to a minimum in order to avoid premature vulcanization. It is also possible to use the slurry method in which the dry ingredients are added to a kneading mixer c containing the copolymer, the resin and the solvent, followed by mixing. Optionally, the dry ingredients can be dispersed in a solvent in a ball mill prior to introduction into the kneading mixer. The oil-soluble thermoplastic resins are generally added directly to this kneading mixer (churn) and are not kneaded into the copolymer on the mixing roll mill. When using modified resins, the unmodified resin can be added to the cement mixer along with enough alkaline material for the modification. The alkaline material can be added as such, mixed into the copolymer or reacted separately with the resin in part of the solvent and added as a solution of the modified resin.

The adhesives have been widely described in the context of its use as an adhesive solution, but they can also, for example for the production of coating compositions jo including viscous cements and sealing and Verstreichmassen be using. The less viscous masses can be applied as coatings directly by brushing, dipping or spraying, for example as a roof covering

909834/1504 bad original

carbon black in an amount which corresponds approximately to that of the copolymer, wherein the coating is non-sticky within J) O minutes, and finally a film with a smooth f'isthaftenden ₃ v; forms enig gloss finish. Depending on the intended use, viscous cements with plastic cohesion can be prepared, for example, by applying high concentrations of the copolymer, adding large amounts of inert filler or using copolymers with high Mooney viscosity, and applied by brushing and spreading with a spatula or a sealing gun. These compounds can be used as putty, sealing and spreading compounds.

When using a non-volatile polymeric solvent is can / ine mass, which resembles a hot melt adhesive, produced and at an elevated temperature can be applied as a viscous liquid, which at normal temperatures returns to the form of a viscous, firmly adhering elastomers. These masses are particularly suitable for sealing and spreading, since there is practically no change in volume during their solidification. A preferred non-volatile one Solvent can be obtained by polymerizing chloroprene in the presence of a relatively large amount of a modifying agent.

At times it is desirable to use cements that Dry to a practically transparent, inconspicuous film, especially when the cement is over the top Application area overlaps with adjacent areas. These cements can be made by all insoluble solid alkaline components with the exception of the one in the modified phenolic resin

909834/1 504 bad or, q, _nal

mixed alkaline constituents, which is soluble, can be omitted ₀ These transparent cements have a higher bond strength "at high temperature than the known opaque cements which contain normal amounts of insoluble solid alkaline constituents besides the magnesium oxide modified resin contains en ο

That Gopolymeren containing from certain groups, carboxyl groups are prepared cements are particularly advantageous for the formation of adhesive coatings on "Vinylharzeno examples are the polymers and copolymer en of vinyl chloride, particularly terpolymers of chloroprene with 10 - 20 G ew _e - $ acrylonitrile and 0.2 - 0.7 G-ewo- ^ methacrylic acid *

• j5 In the following examples, all Quantities based on weight, unless otherwise stated, "

example 1

A preferred copolymer of methacrylic acid and chloroprene for use in the invention Cementing is done in the manner described below ο The methacrylic acid is made in a lot of 1.33 parts per 100 parts of chloroprene used

Bine emulsion is made from the following ingredients

Parts

Chloroprene 13,500

Methacrylic acid --- 180

Diisopropyl xanthogen disulfide 120

Water 18.0 67

Amine Salts of Alkylated Benzenesulfonic Acids 176

■ 50 ITodium salt of the condensate of formaldehyde

and naphthalenesulfonic acid 80

909834/1504

BATH ORIGINAL

The polymerization is carried out "at 40 ⁰ O in a nitrogen atmosphere. It is catalyzed by the addition of 0.2 part of 30% hydrogen peroxide and subsequent addition of 0.05 part portions of a 1% potassium hydrosulphite solution. The addition of the potassium hydrosulphite solution is catalyzed regulated in such a way that the desired polymerization rate is obtained. The polymerization is carried out up to a monomer conversion of about $ 90 at this conversion

• jO "the specific weight of the latex is around 1.080

"at 40 fo for this approach",

The polymerization is then stopped by adding 70 parts of an emulsion of the following composition}

Parts ■ J5 water - 21.0

Sodium lauryl sulfate, paste,

30 io active ingredient 2.0

Sodium salt of the condensate of formaldehyde

and uaphthalenesulfonic acid 0.7

2Q benzene. <~ ._. 45.0

Phenthiazine 0.7

p-t-butyl catechol 0.7

The hydrogen ion concentration of the latex becomes by adding a 2% sodium hydroxide solution Ptt 8 discontinued «, not converted ohioroprene is removed by steam driving in the manner described in U.S. Patent 2,467,769 ", whereupon the copolymer by freeze coagulation in form a thin film based on the US patent 2 187 146 "is isolated in the manner described",

The Mooney viscosity of this copolymer is about.. . - 46-48 (miR-IOO ⁰ O 2.5 minutes) _β The analysis shows that the copolymer contains from about 0.45 $ methacrylic acid (0.24 io Caroxylgruppen) ,,

-. , _tA r «, BAD UP! NAL

909834 / tS (U

In the above-described part, when using larger or smaller amounts of methacrylic acid ■ ("based on chloroprene) or by changing the conversion "For a given ratio of chloroprene to methacrylic acid, copolymers are produced which contain different" amounts of methacrylic acid. By changing the amount of modifying agent the viscosity of the polymer can be adjusted. The isolation of the "in this polymerisation process Copolymers produced can be freeze-coagulated be made without prior p ".- setting" The isolation of the copolymer from the latex by freeze coagulation can also be carried out after the p ^ value has been reduced to approx

"■■ 8 each has been set to

Cements are made from the copolymer according to the following recipe manufactured

■■ · - '" parts

Copolymer 100

Metal connection as in Ta-

■■; ■■ - ■ "'" belle I

Resin reactive to heat

(as in example 2) 45

! Eoluene 165

Ethyl acetate 165

Hexane 165

All ingredients are put in a cement mixer, the rolled will j Ms become a smooth solution has formed

Test bonds are produced from the various adhesives in the manner described in Example 4. To illustrate how quickly the bond strengthens, the strength the bond in kg / om after 1 hour, 3 hours and

909834/1504

8AD ORIGINAL

one day "determined" the strength of the bond "at 10O ⁰ C and 121 ⁰ G is also determined 7 days after the production of the bond" (after the bond has been held for 7 minutes at the temperature mentioned) corresponding values are given for a common gialoroprene cement.

Table I. (a) MgO ^(1st
5 Bonding CaO
7th (kg / cm) Strength of ⁰⁾ MgO
10 öaS
9 MgO
5

metal

Parts -. 5 5 10 7 9 i ^a )

At 24 ⁰ C

Time after
Bonding

1 hour 0.3 1.2 2.1 1.8 1.1 1.4 0.13

3 hours 0.6 2.5 3.6 3.6 3.6 2.1 0.36

1 day 1.5 5.9 7.7 5.9 5.0 4.6 3 ₉ 6 after 7 days

10O ⁰ C 0.11 1.5 2.3 1.8 0.43 03.45 0 ₉ 23

121 ⁰ G. 0.13 1 * 7 1.5 1.7 0.36 0.32 0.21

a) Usual polychloroprene cement for comparison purposes b) 5 parts of ZnO additionally used in the mixture

The table above shows the excellent results recognize the when using magnesium oxide as an alkaline material both in terms of the rapid formation of the bond and in terms of the strength of the Bonding at high temperatures were achieved «. Cements, which contain calcium oxide or calcium sulphide result in rapid formation of the bond and at high temperatures Strengths of the bond that are slightly better than when using the usual polychloroprene cement s are received »

909834/1504 «0 or» ««.

■ ". ■■■ - 15 -. ■

A two-component cement is produced as follows!

100 ropes of the polymer to be investigated are dissolved in 160 parts of ethyl acetate and 160 parts of hexane. Έίηβ resin solution is prepared containing 160 parts of toluene oil, 45 parts of the heat reactive resin, 1 part of water and various amounts of various alkaline materials listed in Table I (b). The "two solutions are mixed in the cement mixer" The results of the various tests are given in Table I (b).

Table I (b)

strength the Bonding (kg / om) (a) metal MgQ PbO MgO + PbO Parts 5 28 5 28 At 24 ⁰ O 0.13 Time after bonding 0.36 1 hour 2.0 1.8 2.5 3.6 3 hours 3.4 4.3 1 day - ^: 6.6 8.0 6.3 0.23 Do T days * 0.21 10O ⁰ G 2.5 4.6 2.1 121 ⁰ Gf 1.5 2.1 2.0

(a) As in Table I (a), repeated here for comparison.

Example 2

This example illustrates the manufacture of the adhesives according to the invention by mixing a customary Polyohloroprens with an Öhloro * pren-methacrylic acid-0opolymeren with a relatively high acidity. regehalto ..-. ': ■■

909834/1504 badomow «.

A chloroprene-methacrylic acid copolymer is prepared essentially by the polymerization process described in Example 1, except that 4.7 parts of methacrylic acid are used per 100 parts of chloroprene. If the isolation of the fjopolymeren by stripping the unreacted monomers with steam, by passing through an ion exchange column, wherein the p _H ~ value is brought from 2 to 7, concentration at 40 $ Solids and Gefrierkoagulierung. The copolymer contains about 1.6 $ bound methacrylic acid (0.83 $ carboxyl groups) ο This product is hereinafter referred to as copolymer A »

A cement made from common polychloroprene and modified Resin, hereinafter referred to as adhesive A,

■ J5 is prepared by adding to a conventional Kautschukwalzmisoher a) 100 parts of a rapidly crystallizing chloroprene polymers (prepared by the polymerization of chloroprene at 10 ⁰ C in the presence of a redox catalyst and Dodeoylmeroaptan)

b) 4 parts of magnesium oxide,

c) 5 parts of zinc oxide and

d) 2 parts of 2,6-di-t-butyl-4-phenylphenol are rolled together «, about 111 parts of this premix are with 156 parts of hexane, 156 parts of toluene, 156 parts of acetone, 45 parts of a phenolic resin formed by condensation of 1-2 moles of formaldehyde with 1 mole of p-t-buthylphenol was prepared, and 0.5 part of water was added to a cement mixer »This Ingredients are mixed until the mixture has a smooth appearance.

Different amounts of the copolymer A are in Samples of Adhesive A dissolved to make a series of cement samples to manufacture increasing amounts of the

909834/1504

Gopolymer A contain »These cements are sealed in The composition of these cements and their demixing properties are kept in cylindrical containers are listed in the following Table II «The segregation is given in percent and defined as follows 3

^ -C _{10 -U 4et} v, "v, height of the clear upper Schioht /. Segregation = _{e of the Plfo e} - *

Table II

Sample oil polymer A, Grew _e - $ MAA * - ^c / o segregation

Parts / 100 parts units in after 43 days

Polychloroprene the polymer at 25 - 27 0

mixture

2A .0 (Control) 0.0 81 2 B 3 0.05 52 " 20th ■ 6 0.10 2D 12th 0.19 9 ##

"... '. ■ * MAA = MetJiaoryl acid ■

** Traces of undissolved polymer A were in these Mixtures detectable

Samples 2B, 2C and 2D, which contain the chloroprene-methacrylic acid copolymer A, contain 0.0, 3, 0.05 or _e fo öarboxyl groups and show a considerable improvement in terms of separation in the ..- even with the lowest concentration of methacrylic acid units. Compared to control sample 2A, which of course does not fall within the scope of the invention ο

": Example 3 '■,

About 1 part of the copolymer A according to Example 2 is dissolved in 8.7 parts of toluene. The toluene solution is

909834/1504

then in two different amounts according to adhesive A Example 2 added * The composition of the samples and the demixing behavior are shown below , given in Table III "

Table III .

Sample Oopolymeres A ₉ öew _o - ^ MAA- $ segregation

Parts / 100 file units after 42 days. Polychloroprene in the poly "at 25 - 27 C

______________ mix

3A 0 (control) 0.0 ■ 62

3B 3 0.05 (0.0 3g CSOOH) 9

This example "confirms the results obtained according to Example 2 and suggests that the" mixing of the samples of this example is appropriate. used method is more effective than that of Example 2 applied "It is to be noted that traces of undissolved Gopolymeren A in the samples C and D were feststellibar of Example 2 _s a sign that the full advantage has been achieved the Ohloropren-Hethacrylsäure copolymers nioht _a

Example 4

Approximately 23 g of a rapidly crystallizing Polychloroprene (prepared by the polymerization of chloroprene at 10 G in the presence of Dodeeylmercaptan and a redox catalyst), 2.0 g of Example 2 Uethacrylsäure chloroprene copolymers A, 1.0 g of magnesium oxide, 1 ₉ described 25 g of zinc oxide and 0.5 g of 2,6-dit-butyl-4-phenyl phenol are kneaded for 10 minutes on a conventional laboratory roller. The polychloroprene compound contains about 0.07 carboxyl groups.

909834/1504 ^BAD

The same mixture is only used for outdoor purposes j »" at which, however, 25.0 g of the rapidly crystallizing Polyohloroprens are used and no Chloroprene-MetJaacrylic-acid-Go polymeri sat trains set zt is made in the same way

22.5 g of the in example 2 described phenolic resin dissolved in 80 g of toluene »To. this solution is 2.0 g of magnesium oxide and 0.5 cm of water added · The mixture is 2.25 hours The toluene solution of the modified stirred at room temperature Resin is diluted with 80 g of hexane and 80 g of ethyl acetate * The diluted solution is divided into two equal ropes divided into three sharks and flasks that are provided with a stirrer.

The two mixtures produced on the roller mixer, the copolymer mixture and the 7ergXeichsmixture, are placed in separate flasks and stirred for 64 hours over a weekend, during which smooth adhesive solutions are formed. The Brookfield viscosity of the adhesive solution produced from the copolymer mixture is 1300 Cp. (50 rpm, spindle Ir ₀ 5 -) * The viscosity of the comparison sample is 6? 2 Gp *

Test bonds are made with the two adhesives by wearing three adhesive coats on two 2 _t 54 cm "wide strips of unfinished canvas Br. 10 sxx £, allowing about 30 minutes to pass between each application. Before the final coats are dry, the strips are pressed together firmly with a hand roller in order to establish good contact.

903034/1504 BAD original

The test machine can be attached. The samples are pulled apart at a speed of 5.08 cm / minute. The force required to separate the samples is measured. When the strength of the bond is determined in this way at 8O ⁰ C, a value of about 1.25 kg / cm and for the comparative sample, a YiTert of only 0,54 kg / cm is for the cement containing the copolymer mixture obtained .

The separation of the two adhesive solutions is carried out at room temperature in the manner described in Example 2 measured · The results are shown in the table below IV listed «

Table IV.
sample

15 comparative sample

Copolymer blend

The strength of the bond at high temperature and the results with regard to segregation are clear the superiority of the adhesive 2Q according to the invention recognize substances via known adhesives.

Example 5

Two emulsions are made up of the following ingredients in agitator tanks in a nitrogen atmosphere manufactured"

5A 5B

Chloroprene 420 g 420 g

Methacrylic acid 18 g

Dodecyl mercaptan ■ 2.2 g 2.2 g

Water 727 g 727 g

909834/1504

^BAD OR1G1 _NAL

8th Segregation, f ° Days 4 days Days 15 days 29 60 54
0 50 60
0 ^ 1

Amine salts of alkylated

Benzenesulfonic acids 11 g Hg

.- "'..- sodium salt of the condensate of

Formaldehyde and naphthalenesul-

Fonsäure 5.9 S 5.9 g

The emulsions are cooled to about 20 ° C. The polymerization is started by adding 5 drops of cumene hydroperoxide and from several cnr of a liquid aqueous / triggered by sodium hydrosulphite solution. It is made by adding a liquid, watery drop by drop Sodium hydrosulfite solution continued. During the course of the two polymerizations, emulsions, which were made in separate vessels as a substitute for the chloroprene monomer consumed by the polymerization was added. These emulsions have the following composition: /

Chloroprene 9 ° o g

Dodecyl mercaptan 2.7 g

Water 611 g

Amine salts of alkylated benzenesulfonic acids ^ Io g

Sodium salt of the condensate of formaldehyde and naphthalenesulfonic acid 9 S

The polymerization temperature is increased by external cooling kept below about 20 ° C with an ice bath. If the specific gravity of the polymer mass to I, o5ö rises, which corresponds to a conversion of 80 # of the monomer corresponds to polymer, an emulsion of a toluene solution of phenthiazine and di-t-butylhy-Jo droquinone added. To further polytuerisation back off.

909834/1504 _BAD

The "two polymers are isolated from their latioes by neutralization with aqueous aqueous sodium hydroxide, driving the unreacted monomer with steam and drying on a dry drum." The copolymer produced from emulsion 5A (hereinafter referred to as copolymer 5A) has a Mooney viscosity of about 14 (ML-2.5) and contains about 1 "ß, bound methacrylic acid (0.52 ° ß> carboxyl groups) o The polymer made from Emulsion 5B (hereinafter referred to as comparative pro" be) has a Mooney viscosity of about 28 (ML-2.5).

Cements are prepared from the Gopolymeren 5A and the comparative polymers by 25.0 g of the polymer, 1.0 g of magnesium oxide, 1.25 g of zinc oxide and 0.5 g 2 _t 2 '' - methylene "bib (4-methyl -6-t-l-butylphenol) mixed on the roller mixer for 10 minutes,

11.25 g of the phenolic resin described in Example 2 are dissolved in 40 g of toluene in a stirrer "container." 1 g of magnesium oxide and 0.25 om of water are added to this solution. The mixture is "stirred at tree temperature for 2.25 hours» The toluene solution of the modified Resin is diluted with 40 g of hexane and 40 g of ethyl acetate. The one produced on the roller mixer Mixture of the copolymer 5A is added to the resin solution and 64 hours over a Y / ochenende "moved where" at a smooth adhesive solution is formed »This cement has a Brookfield viscosity of 173 Gp "(100 Rpm, spindle Ur. 3) »

In a second vessel is made from the reference polymer prepared mixture processed into a cement in the manner described above. This Cement has a Brookfield viscosity of 148 cp

9Q9834 / 15CU

2er cement produced from the Gopolymeren 5A shows no segregation when 90 Days "is stored at 25 ° 0 ο Even after 90! Days at 5O ⁰ G does not Entmischimg instead of" contrast shows the cement produced from the Vergleiohspolymeren "after about 18 : Days "at 25 ⁰ C a 40-sequence segregation and already after 13! Pages at 50 ⁰ G a 75 ^ ige segregation.

Despite its low Mooney Yiskosität 5k of the cement from the copolymer produced has a Sohälfestigkeit of about 6.25 kg / cm at 25 ⁰ C, of 3.93 kg / em at 10O ⁰ G and 0.89 kg / om ⁰ at 150 C, while the liergleiehszement a peel strength of 4 »47 kg / om at 25 ° G 'of only 0,36 kg / om at 100 G ⁰ and as 0.18 kg / cm at 15O ⁰ C.

Two further cements are produced from the copolymer 5A, the. Only differ in the amount of Phe- --- ': nelharz it contains. Used instead of the above Lall 11.25 g of resin, these cements are prepared using 2 ^ 5 g UNOE t6 _s 25 g resin. None of these cements shows a separation over a period of several weeks' Cement with 16.25 g resin has a shear strength of x about 2.68 kg / cm at 10O ⁰ C.

■■■■ "" Example 6

A copolymer of chloroprene and methacrylic acid is made essentially to that described in Example 1

Manner with the exception that 1) about 1.36 5BeIIe methacrylic acid and 0.19 parts per 100 Dodeoylmercaptan chloroprene ropes are used, and 2) the polymerization is carried out at 1O ⁰ C .. The poly-mers is -30 to in Example 1 described manner a -. :: Finally, neutralization with aqueous Uatriumhy-

909834/1504

BATH ORIGINAL

droxyd isolated. The isolated copolymer has a Mooney viscosity of about 150 (MI-2.5) and contains. about $ 0.46> found methacrylic acid ( $ 0.24> carboxyl groups). .

Aue the copolymer is prepared in the manner described in Example 5, a cement using 11 ₉ 25 g of phenol resin "The Brookfield Viskosiiät this cement is about 6000 Cp _0" at Räumtemperatur ₀ The very high viscosity of the cement reflects the high Mooney viscosity the copolymer again ,, This cement can be with the brush on ge painted. After einer.lagerzeit of 64 days it shows no signs of demixing "His KIeTDfestigkeit" at 125 ⁰ C "is about 6.07 kg / om. This value is outstanding. At 125 ^° C., the strength of a bond with a comparative adhesive which had been produced from a conventional chloroprene polymer is less than 0.18 kg / om-β

Example 7

A copolymer of chloroprene and methacrylic acid is prepared essentially in the manner described in Example 1 "except that 1) about 2 parts of methacrylic acid and 0.8 parts of diisopropylxanthogen disulfide are used per 100 parts of chloroprene, and 2) the polymerization" at about 15% ⁰ C is carried out. The copolymer is isolated in the manner described in Example 1 "including neutralization with aqueous sodium hydroxide. The isolated copolymer has a Mooney viscosity of about 26 (ML-2.5) and contains about 0.68 # bound methacrylic acid (0.36 rf> carboxyl groups) β

In the manner described in Example 5, a Ze- 909834/1504 s _{AD 0Rle} , _NAL

• ■ - 25 - ■■■■ '.. ■

ment made from the copolymer using 11.25 g of phenolic resin. The Brookfield viscosity of the cement "is 2070 Op ₀ (spindle Ur ₀ 4). After 90 days the cement shows no signs of segregation. The strength of the adhesive bonds with this cement" is 7.5 kg / om at 25 ⁰ 0.6 , 07 kg / ^{cm at 80 0 0} , 4.47 ^{kg / cm at 100 0 0} and 2.14 kg / cm at 125 ° 0.

Similar results are obtained when the solvent mixture from equal parts by weight of toluene, ethyl acetate and hexane by the same amount by weight a solvent mixture is replaced, which from 35 Parts by weight of Laokhenzin and 65 parts by weight of methyl ethyl ketone consists. In the manufacture of these cements, the phenolic resin is mixed with magnesium oxide in the gasoline solvent before the addition of the methyl ethyl ketone modified.

Example 8

A Oopolymeres of chloroprene and methacrylic acid is generally prepared in the heschriehene in Example 1 except that 1) 1.33 parts of methacrylic acid and 0.33 parts per 100 parts chloroprene Dodeoylmeroaptan be used, and 2) the polymerization hei 10 ⁰ O The material is isolated in the manner described in Example 1 after the addition of aqueous sodium hydroxide. This copolymer has a Mooney Yiskosität of 40 (ML-2.5), and contains about 0.45 # bound methacrylic acid (0.24 i "Oarboxylgruppen).

Cement is produced from this copolymer by adding 25.0 g of the copolymer produced in this way, 11.25 g of the phenolic resin used in Example 2, 2 g of magnesium oxide, 1.25 g of zinc oxide, 0.5 g of 2.2'- Methylen-bie (4-methyl-6-t-butylphenol), 40 g toluene, 40 g '909934/1504

BATH

Ethyl acetate and 40 g of hexane in a stirrer The mastication of the copolymer is omitted. This mixture will stirred for about 16 hours, where "at sioh a smooth time -ment with a Brookfield viscosity of 654 Op »Mldet. This cement showed no segregation during a period of 56 layers. He forms disguises with following strengths »

Temperature, ⁰ O 25 80 100 125

Thickness of the bond, kg / om 7.5 4.64 3.75 3 _f 04

This example illustrates the ease with which the cements can be produced from the products according to the invention »when carrying out this However, processes are preferably freshly made Polymers used »The omission of rolling "Does not significantly affect the segregation and the strength of the bonds

Example 9

Two copolymers of chloroprene and methacrylic acid (9A and 9B) are prepared essentially in the manner described in Example 1. Both polymerizations are carried out using 1.33 parts of methacrylic acid and 0.89 parts of diieopropylxanthogen disulfide per 100 parts of chloroprene differ in that it is carried in a case (copolymers ^ 9A) "at about 15 ⁰ C and in the second Pail (copolymer 9B)" at 4O ⁰ C. the isolation of the copolymers is carried out in the manner described in example 1, including additional of aqueous sodium hydroxide

909834/1504

The Mooney viscosity (ML-2,5) "is about 52 for the copolymers 9A (" polymerized at 15 ⁰ C) and about 49 (polymerized at 40 ⁰ O) for the copolymers 9B ο Both contain about 0.45 ° f bound methacrylic acid ( $ 0.24 carboxyl groups).

Two cements are produced from the copolymers 9A and 9B in the manner described in Example 4 * Both cements show good segregation behavior «The Viscosity and the strengths of the bonds with them Cements are listed below. The values for a reference cement made from a conventional chloroprene polymer are made for comparison

Table V

Cement—]
15th

Cement-
sample Brookfield
Viscosity, strength
kg / cm the Bonding, 25 ⁰ C Op. (Spindle
No. 4) 25 ⁰ O 80 ⁰ O 100 ° C 1 ,1 Oopolymer 9A 580 5.7 4, 5 3.0 1 , 4 polymer 9B 550 7.0 4, 3 2.7 1 , 14 Comparative cement 520 7.0 0, 20th 0.18 0 Example 10

This example illustrates the preparation of a "transparent" cement, except the magnesium * - oxide modified phenolic resin not containing the alkaline component of about 25 Copolymeren.5A of Example 5 and 0.5 g of 2,2 g ^{f-methylene-bis} (4 -methyl-6-tbut-ylphenol) are mixed for 10 minutes on the roller mixer. In a three-necked flask, 11.25 g of the phenolic resin described in Example 2, 1.0 g of magnesium oxide, 0.5 g of water and 40.0 g of toluene are stirred for about 2 hours. About 40 g of ethyl acetate and 40 g of hexane are added to the modified resin solution, 909834/1504

BATH ORIGINAL

whereupon the mixture prepared on the roller mixer is added. The whole mixture is "moved up" a homogeneous cement is formed. The liquid cement has a cloudy appearance, but adhesions are that . made between pieces of clear plastic, transparent,

Connections between sailcloth and sailcloth made with this cement "have typical strengths of about 6.6 kg / cm at 25 ⁰ O, of 3.04 kg / cm at 80 ⁰ O, of 2.14 kg / cm at 100 ° ö and of 0.34 kg / cm at 125 ⁰ Oe in a ähnliohen cement, which is made of a conventional öhloroprenpolymeren, the strengths of the bonds at elevated temperatures are much lower.

Example 11

... This example illustrates the production of a spreading compound or a hot melt adhesive in which the usual volatile solvents for cements through a non-volatile polymeric solvent, that has been obtained in the manner described below, be replaced "

A common polychloroprene emulsion. is made up of the following Components manufactured!

Parts

Chloroprene 100

Diisopropylxanthogen disulfide 4.7

Oleic acid 3.8

Gumolhydroperoxyd ■ "0.14

Sodium hydroxide 0.24

Water 133.33

909834/1504

The preparation of the emulsion and the subsequent polymerization are carried out under nitrogen. A solution containing 0.20 parts of ammonium persulphate and 0.006 part of sodium 2-anthraquinone sulphonate in 5.0 parts of water is added to the emulsion while stirring gently. The polymerization is triggered by adding 0.067 part of solid sodium hydrosulfite dihydrate to the system . The polymerization rate is then regulated in such a way that, as required, a solution of 0.01 part of sodium hydroxide dihydrate and 0.000 2 parts of sodium hydroxide in 0.23 part of water is added will.

When the specific gravity of the latex has reached 1.063 at 2O ⁰ O •, the polymerization is the sodium salt of a Containing condensate of formaldehyde and naphthalenesulfonic acid as well as sodium lauryl sulfate, canceled. The polychloroprene is isolated on a double drum dryer that is heated with 5.6 atmospheric steam.

The spreading compound is prepared by adding about 40 g of the chloroprene polymer described above, 50 g of the copolymer 5A of Example 5, 2 g of 2,2' -methylene bis (4-methyl-6-t-butylphenol), 4 g of magnesium oxide, 10 g of tin oxide , 20 g of a low-viscosity chlorinated paraffin oil and 10 g of the phenolic resin described in Example 2 are mixed on a roller mixer. After a rolling time of 20 minutes at 50 ⁰ O , a smooth finish is obtained.

Bin portion of this material is heated to 100 ⁰ O and applied with a spatula to 2 Stüoke fir at room temperature, the shear strength is about 4.2 x ^ dtr bonding Naoh standing for several days kg / om ² --909 834/1504 'bad

"at 25 ⁰ O.

A portion of this material is heated to 50 ⁰ O and to fill an irregular Rissee (approximately 3 mm wide) used in a Tannenholzbret-t of 6.2 mm thickness. The material is applied with a putty knife "after 16 hours" at room temperature, the sealant turns into a soft elastomer that cannot be pulled out of the crack by hand.

Example 12

This example illustrates the preparation of a pigmented coating composition falling within the scope of the invention falls.

A copolymer of methacrylic acid and Ohloropren is in substantially the prepared in Example "described" manner with the 5 excludes that about 2 parts methacrylic acid and 0.4 parts per 100 parts Dodeoylmeroaptan Ghloropren be used and the polymerization at 4O ⁰ O is performed. This amount of methaoryl acid corresponds to 1.05 # carboxyl groups, based on chloroprene. The copolymer is isolated in the manner described in Example 1, including the p "classification, using aqueous sodium hydroxide. This copolymer has a Mooney viscosity of about 84 (ML-2.5) and contains about 1.1 $> bound methacrylic acid (0.57 # carboxyl groups)

A coating composition is prepared by adding 50 g of dieees Oopolymers, 50 g carbon black (Medium Thermal Black), 2 g magnesium oxide, 2.5 g zinc oxide and 1 g 2,2'-methylenebis (4-methyl-6-t-l) utylphenol) about 10 minutes to be mixed on the roller mixer and the Misohung to one solution of a modified phenolic resin is given, 5Q which is prepared in the manner described in Example 4

909834/1504

was presented. The whole mixture is in the cement mixer ■. .- ■■ * ■■ -. treated, Mb them smooth 1st ο

Part of this product is poured onto a polyethylene terephthalate film, on which it is allowed to flow apart under its own weight and to dry. This material dries to a non-tacky surface in about 30 minutes. The coating is smooth and has a uniform off see "On the other hand, a comparison coating was made from a usual chloroprene, sticky even after 2 hours and is only after about 16 hours, a non-sticky surface ₀ The surface of this latter coating is irregular as the surface of the chloroprene-methacrylic acid copolymer coating

The shear strength of a bond that is related to the '; . measured this example produced mass between Kie- ■ Remote boards is made, is about 15.4 kg /

-.-;? . _ _; ■■ - om at room temperatureo

Example 13 -

'., ■ An oleopolymer of chloroprene and methacrylic acid, which contains about -O ^ 24? Έ carboxyl groups, is essentially. oh-en prepared in the manner described in Example 5 with the exception that 1.33 parts of methacrylic acid. ; .., ■; ■■ and 0.3 parts of dodecyl mercaptan are used per 100 parts Ohloropren and the polymerization is carried out at 40 ⁰ G. The copolymer is isolated in the manner described in Example 1 including Pr, setting with aqueous sodium hydroxide «

A cement is made from 25 g of this copolymer on the in 3Ö bit game 4 described way produced with the

90 9834/1 S04 bad original

assume that the solution of the modified with magnesium oxide Phenolic resins in the toluene, hexane and ethyl acetate "be standing en solvent only with the Half of the ingredients used in Example 4 is made.

About 0.25 g of hexamethylene diisocyanate are used in 25 g of the stirred in the above-mentioned adhesive solution, whereupon stirring is continued for about 1 minute. The added diisocyanate serves as a vulcanizing agent and ver - .. Q ! Dessert the adhesion of the cement to non-porous substrates.

Using this adhesive, steel to steel and "Formica" to "Formica" joints are made. ( "Formica" is a "high pressure produced laminate reinforced melamine and phenolic resins ₀₎ The substrate to be coated with the cement and with an overlap of 2 square inch bonded" Wax 3 Woohen at room temperature, the shear strengths of the bonds will be noted in the compounds from steel to steel they are approximately

ρ p

12.9 kg / cm at room temperature and about 1.0 5 kg / om at 100 ⁰ O. In the compounds of "Formica" on "Formioa" they amount to about 9.1 kg / om at room temperature and about 0.77 kg / cm ² at 10O ⁰ O ₀

Example 14

This example illustrates the preparation of adhesive solutions using a thermoplastic Harz · «

Two copolymers of chloroprene and methaoryl acid are prepared essentially in the manner described in Example 1 with the exception that about 1.5 parts methaoryl acid and 0.89 parts diisopropylxanthogen disulfia are used per 100 parts of chloroprene.

909834/1504 bad orig, _nal

The "two Oopolymeren differ in that the one" at about 1O ⁰ O (copolymer 14A) and the other "is polymerized at about 40 ⁰ C (Oopolymeres 14B). The Mo oney viscosity (ML-2.5)" is about 44 for. ■ the oil polymer 14A and about 46 for the copolymer 14B ". Both copolymers contain about $ 0.54 of bound methaoryl acid ($ 0.28 carboxyl groups)"

Adhesive premixes are produced from these "two copolymers by using the following components IC) parts to be mixed on the roller mixer:

Parts

Copolymer 100

Magnesia 4

Zinc oxide 5

4.4 ^l ~ thiobis (6-t-butyl-m-cresol) 2

Die_ premixes are placed in Rührwerksgefäße, ■■■ '45 parts of a thermoplastic, terpeninodifi-.zierten Pormaldehyd phenol resin ( "Durez 1260 3", melting point 15Q ⁰ C, soluble in niohtpolaren Lö'sungsmitteln prepared by Durez Division, Hooker Elektrochemieal Co ₀ ) and each contain 200 parts of toluene, hexane and ethyl acetate »The two mixtures are stirred until smooth, homogeneous cements are formed» The Brookfield viscosity of the cement made from the copolymer 14A is about 280 Cp ₀ (spindle Ur · 2, 12 rpm) and about 330 cp ₀ for the cement made from the copolymer 14B.

The cements are used to create adhesive bonds between sailboats and test them at different temperatures. Typical values are listed in the following table together with the results obtained with a comparison cement that has been approved by the other

■ ORiGiMAL BATHROOM

90983Λ / 150Α

159421ε

whose cements differed only in that it was made with a common chloroprene polymer.

Table VI Strength of Strength of Tempe Strength of Bonding Bonding rature Bonding with cement with comparison with cement made of copoly- cement, made of copoly- merem 14B, kg / cm . merem 14A, kg / cm kg / cm 2.5 0.98 60 2.5 2.1 0.18 80 2.3 1.3 0.0 9 100 1.6 0.89 0.09 120 1.1

As already mentioned, the cements according to the invention have which contain thermoplastic phenolic resins have a tendency to gel when stored. Cements of the type made according to this example remain in usable condition for a period of 2-6 weeks.

The stickiness of the cements produced from the copolymers 14A and B is similar to that of the comparative cement was observed. Thin films of the cement remain sticky for 5-15 minutes. Thick films remain Sticky for 10-25 minutes.

The rate at which the strength of the adhesive bond increases with time at 24 ⁰ G is measured for the cements produced in the manner described. With each of the three cements, including the comparison cement, connections are made between canvas and canvas, whereupon the strength of the bond is measured at increasing time intervals after bonding. The results are compiled in the following table. They clearly illustrate

909834/150 ',

the very high speed at which the strength of the bonds produced with the cements according to the invention increases ₀

Table VII

Time after gluing Canvas with canvas

1 hour

10 '-3 hours 1 day
1 week

strength the bond kg / cm Comparison
cement Cement out
Oopolymer
HA Cement out
Copolymer
14B. 0.27 2.5 1.4 1.4 3.6 5.2 3.4 4.3 4.3 2.7 4.8 5.0 Example 15 -

Kiel material premixes are made from the copolymer 14A and 14B by mixing the ingredients mentioned in Example 14 on the roller mixer. The premixes are poured into agitator vessels, containing 200 parts of hexane and 200 parts of ethyl acetate. During the same time, 2 batches of a resin modified with magnesium oxide are made, by adding 45 parts of the phenolic resin described in Example 2, 4 parts of magnesium oxide and 1 part of water in 200 parts of toluene for about 6 hours "at room temperature be stirred. One batch of the resin modified with magnesium oxide is placed in each of the vessels 'contain the premix, whereupon the mixtures are stirred Ms smooth cements are obtained. '

The rate at which the strength of the Klebyer bond increases at 24 ⁰ O is used for. these two cements and measured for a third cement which differs from the other cements only in that it consists of

BATH ORIGINAL

909834/1504

a common oleoprene polymer. With Each of the three cements creates a series of adhesive bonds manufactured from canvas to canvas “The strength of the bond is determined according to different time intervals measured. The results obtained are shown in the table below. They illustrate again the very rapid development of the strength of the bond with the cements according to the invention »

Table VIII

Time after bond

Time after Strength of the bond, 1 Cement out cg / cm I6 0.7 gluing of Cement out Comparative 1.8 Canvas Oopolymer
14A Gopolymer cement
14B 5.7 1 hour 2.3 1.8 5.5 3 hours 3.2 3.6 1 day 4.1. 4.1 1 V / o marriage 4.6 4.6 . example 1

An emulsion is made from the following components χ

Chloroprene 980

Acrylic acid 20

Diisopropyl xanthogen sulfide 9

Triäthanolammoniumäoäeoylbenzenesulfonat (60 $ solution) 20

'' Sodium as the condensate of formaldehyde and naphthalene sulphonic acid 6

The emulsion is held under nitrogen at 40 ⁰ O heated "After addition of 1 part by weight öumolhydroperoxyd the polymerization is initiated by adding a solution containing 1 part of sodium hydrosulfite, and 0.2 parts of sodium hydroxide in 100 parts by volume of water. The polymerization is carried out by adding this dropwise

909834/1504 ^ß * D

- 37 -

Solution kept in motion, Ms the specific gravity The emulsion is 1.075 "($ 88 mono conversion). A total of 24 parts of the solution are required Polymerization is accomplished by adding 15 parts of a Aborted emulsion containing the following ingredients contains Γ

Parts

Phenthiazine 1 p-t-butyl brenzoateohin 1 toluene 64.2 water 29.85 Sodium dodeoyl sulfonate 2.84 Sodium salt of the condensate of form aldehyde and naphthalenesulfonic acid 1

The, _pH value of the emulsion is adjusted by addition of a sodium hydroxide solution 2 $ on. 8 The excess chloroprene is removed and the polymer is isolated in the manner described in Example 1. The isolated polymer has a Mooney viscosity (ML + 2.5) of 32 "at 100 ° 0. The content of methacrylic acid, determined on a reprecipitated sample that contains no unreacted monomer," is 0 ₉ 15 $ (carboxyl content 0.08 #) «■

The polymer becomes a mixture with the following additives processed $

! Bearings

ι polymer 100

Magnesium Oxide '' 8

Zinc oxide 5

H-phenyl-2-riaphthylamine 2

57 g of the mixture, together with 20 g of that used in Example 2, are heat-reactive Phenolic resin and 0.5 οτα. Water to 290 cur of a Gemisohes of 990 om ^ toluene, 96Ο Qnr ethyl acetate and

9834/1504 ORIGINAL BATHROOM

1305 cur hexane given · The mixture is rolled until sioh has formed a smooth cement.

For comparison, a cement in the same V / else, but using the used in Example 2 übliohen Ghloroprenpolymeren · samples of the cements are aged in a hot 50 ⁰ C held Y / ärmesohrank · After 2 weeks, the cement which the !! "Contains common chloroprene polymers, separated in two soles" The cement made with the copolymers containing carboxyl groups is stable for an infinite period of time "

Example 17

Two emulsions are made up of the following ingredients manufactured! .

Chloroprene

2,3-dichloro-1,3-butadiene
Methacrylic acid

Diisopropylxanthogen disulfide 20 Was β er

Triethanolammonium dodeoylbenzene sulfonate

(60f & Lge aqueous solution] 20 20

Sodium al ζ dee condensate of formaldehyde and naphthalenesulfanic acid 6 6

The polymerization is carried out as described in Example 16 Ton · Weis · his carried out to a monomer conversion of 85 # · He isolated polymers adhere to Mooney viscosities from 56 hzw. 60 and contain 0.54 hzw. 0.45 # Methacrylic acid corresponding to a content of carboxyl

30 groups of 0.28 or 0 _? 50 ffi.

Parts A. B. 690 787 290 200 20th 13th 9 9 1150 1150

90983471504

-.39 - '■.

Cements made from these polymers based on the Tested as described in Example 16, "stay." infinitely long staMl (d "ho they" do not form separate Phases)

Example 18

Two emulsions are made from the following ingredients *

Acrylonitrile
• jQ chloroprene

LIe thacrylic acid e

Diisopropylxanthogen disulfide

water

Triethanolammonium dodecylbenzenesulfonate ■ J5 (ÖOjSige aqueous solution)

Sodium salt of the condensate of formaldehyde and uaphthalenesulfonic acid

The polymerization is substantially in the Example 5 teschrielbene Tieise performed with the Ausnähme that the temperature is kept hot 4O ⁰ C. Polymerization of the Emulsion A Emulsion B is triggered and the "continuously added to the emulsion A during the polymerization the oxidizing component of the catalyst is contains a 2 $ aqueous solution of potassium persulfate containing 0.1 $> Uatrium 2-anthraquinonesulfonate. As a reducing component, a 0.5% aqueous sodium hydroBUlfit solution is used which contains 0.2% of sodium hydroxide. The polymerization is carried out with a monomer conversion of $ 80 and is added by adding a steel emulsion containing the following components:

Parts A. O, B. 19.8 - 29.4 1, 50 0.8 0, - 0.3 55 50 50 1.2 1 0.5 5

90983471504

■ -. Parts

2,6-di-t-t> utyl-4 ~ phenylphenol 39.3

Toluene 25.6 phenthiazine 1

2,5-di-t- "butylhydroehinone. 1

Water 30 I sodium ao de oyl sulfate 2.8

Sodium salt of the condensate of formaldehyde and naphthalenesulfonic acid .1

The Ρττ value of the emulsion is determined by adding 2%

xl

aqueous sodium hydroxide adjusted to 7-8. After removal of unreacted monomer, the polymer is isolated by freeze coagulation in the manner described in US Pat. No. 2,187,146. The isolated copolymer has a Mooney viscosity (ML-2.5 , 10O ⁰ C) of. about 51 "It has the following composition, expressed in weight percent of the Monomerens found

Chloroprene $ 90.2>'

Acrylonitrile '' $ 9.4

Methacrylic acid. $ 0.4

The content of carboxyl groups found "is 0.21 Gewe-ji '. The polymer premix is made up of the following components manufactured:

Parts

Copolymer 100

2,2'-methyleneMs (6-t-'butyl-p-cresol) 2

Magnesia 4

Zinc oxide .5

A resin solution of the following composition is prepared *

Resin (as in Example 2) 10

Methyl ethyl ketone 60

Toluene. 65

Magnesium Oxide 1

909834 / 1B04

- A cement is made by adding 25 g of the polymer premix is dissolved in the resin solution. The cement remains stable even if it is 7 months "at room temperature is left standing. A comparative cement made from a chloroprene-aorylnitrile copolymer which does not contain copolymerized methacrylic acid, demisos within a day. If that Chloroprene-aorylnitrile-methaorylic acid copolymers for Production of a similar cement is used,

• JÖ where Jedooh no resin is added, is the cement unstable and gels within 2 months at tree temperature.

Another cement is made from the copolymer as follows manufactured! The following components are used in dispersed in a ball mill »

horny

Magnesium Oxide "4

Zinc oxide. 3.3

Toluene 14

2,2 · -Methylene bis (6-t-butyi-p-cresol) 2

This dispersion is added to a solution of the following composition »

Gopolymer 100

Resin (as in Example 2) · 40

Methyl ethyl ketone '^; . . 232

Toluene 218

, The strength of gluing from Segeltuöh to Segeltuoh is determined at room temperature. The following values are determined j

- Age of the gluing k «/ om

4 hours 2.1

1 day 7.7

909834/1504

8AD ORIGINAL

The strengths yon Verkletungen of canvas on an upper part of Sohuhen based on polyvinyl chloride were determined as follows%

Age of Temperature, O kg / cm Bonding 4. minutes 25th 1.9 4 hours 25th 2.1 1 day 25th 2.7 7 days · 25th 3.9 7 days 70 0.6

Suitable vinyl monomers are terms of the general journal OH ₂ = OR-COOH, GH ^ = GRc-CX) B ¹ and CH ₂ = CR "'- ON, where R, R", R "and R ^M " alkyl, aryl, cycloalkyl or aryl alkyl and R and R "can also be hydrogen, wherein jedooh R ¹ and / or R ^tt ALB a carboxyl substituents, and R ^{l! l} also a carboxyl group as substituents must fill · are preferably Aorylsäure and their lower (C.- C «) - alkylsu'bs1; ituated homologues, especially methacrylic acid, because they are easily obtainable and easy to use with chloroprene copolymers! long "known that they co-polymerize with chloroprene, as stated in the US Patent Declarift 2066 ·

In addition to chloroprene, at least one further comonomer, which does not contain any oil, can also contain but with chloroprene copolymerization is - * «rtr, in an amount "up to half the weight of the Ohio rod be used. Suitable comonomers are vinyl sulfites aromatic yeasts such as styrene, Yinyltoluenes and vinylnaphthalenes, esters and nitriles of acrylic acid and methacrylic acid, such as methyl methaorylate and aorylnitrile, and yer "binäungen, aie .conjugated

909834/1504

Contain double bonds, such as 1,3-butadiene, isoprene and 2,3-diclilor-1,3- "butadiene _e The copolymers can optionally be prepared in the presence of sulfur or sulfur dioxide - In this case the copolymers contain polysulfide or sulfonyl endings»

909834/1504 BADORiQiNAL

Claims (1)

Claims 1) Adhesive mixture based on chloroprene polymers and oil-soluble phenol-aldehyde resins and containing magnesium oxide and an organic solvent, characterized in that a chloroprene polymer is used as a chloroprene and a monomer of the aerylic acid type, in particular methaoryl • acid, obtained product is present and that at least two parts of magnesium oxide per 100 G-eWe parts of the Ohloroprenoopolymeren are present in the mixture. 2) Further configuration of the adhesive mixture according to Claim 1, characterized in that in addition to or instead of the magnesium oxide, an equivalent amount of calcium oxide, calcium sulphide and / or lead oxide was present in the mixture 5.1 Adhesive mixtures according to Claims 1 and 2, characterized characterized in that the Ohloroprene copolymers Contains 0.1-0.4% by weight of carboxyl groups » 9 0 9834/1504 _AQ (Art 7 Paragraph 2 No. I Clause 3 of the Anderunaeaea. V. 4.9.