BE670691A - - Google Patents

Description

       

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  New bisphnols and polymers derived from it.



   The purpose of the presenta is to rectify a material error made in the execution of the specification.
On page 32, line 8 from the bottom of the page, the number "1" should be replaced by the number "14" in order to read the said line as follows: "The product of example 14 is identified talk to..."
This correction of an obvious typing error is justified to put the sentence in agreement with the title of the example studied.



   The same correction is to be made on page 32, lines 1 and 5 from the bottom of the page.



   The Administration is authorized to attach a copy of this letter to the copy of the corresponding patent.



   For the good rule, it would be pleasant for us if you would kindly acknowledge receipt of the present stipulating that the rectification is admitted to be valid as of right.



   We join to. this presents in fiscal stamps the regularization tax provided for in article 1 of the Royal Decree of 29 August 1926 amended by article 6 of the Royal Decree of 30 June 1933 and 25 November 1939.



   Reading you, we ask you to accept, Mr. Minister, the assurance of our highest consideration.

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  "New bisphenols and polymers derived from it"
The present invention relates to novel bisphenols and condensation polymers made from these bisphenols,
It has hitherto been known to condense phenols with aldehydes and ketones to produce bispbenols. The bisphenols thus produced, however, have their phenolic moieties attached to a single carbon atom. The close proximity of the phenolic moieties has limited the control which can be exerted on the properties of the known bisphenols and condensation polymers produced from these bisphenols.

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 drown.

   Methods have been proposed for putting the phenolic moieties on different carbon atoms, such as for example a double Pries transposition of the es-
 EMI3.1
 dibasic acids (phenolic acids) but such methods have not been of practical use.



   The 'aims of the above invention are therefore to provide t
 EMI3.2
 duo new bisphenols in which the moieties are attached to oex-bona atoms dLi ± 6i'un.bsj - a practical process for the production of bishenols in which the phenolic portions are attached to different carbon atoms; - condensation polymers containing
 EMI3.3
 bisphenol fractions in which the phenolic moieties con 'fixed on different carbon atoms; -. bisphenol condensation polymer backs
 EMI3.4
 ft., y {.nt dOI1 high glass transition temperatures and ungrando inherent toughness.



  The deandere & has just discovered that one manufactured bisphenola having phenolic portions cur '\ e'J rto! ICO duo carbon different by putting in contact: a cyclic organic compound comprising unconjugated double bonds and at least a quantity of a phenol with an acid catalyst
 EMI3.5
 alkylation.



  The expression "cyclic organic compound
 EMI3.6
 having unconjugated double bonds ", as used herein, relates to cyclic dienes having double bonds separated by more than one carbon atom and relates to cyclic compounds which

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 transpose under acidic conditions or at elevated temperatures to give a diene having unconjugated double bonds.



   Cyclic compounds which are found to react with phenol to give new bisphenols having the phenolic moieties attached to different carbon atoms are
 EMI4.1
 
 EMI4.2
 1,4-dimethylene cyclohexane
 EMI4.3
 
 EMI4.4
 4-vinyl-oyolohexane
 EMI4.5
 
 EMI4.6
 ie dicyclopentadien
 EMI4.7
   alpha. - pinene
The reaction shown for phenol and
 EMI4.8
 the 1, L.dimethylen, e cyclohexane proceeds, in general as follows
 EMI4.9
 

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 EMI5.1
 Catalyst, # acid CHx CH 2 r \ -OH + CH2. os) = ci% acid iio 8 # "\ ¯ / I0 - /
This benefit is the bisphenol of 1,4-dimethylene-cyclohexano.



   Phenol and 4-vinyl-cyclohexane react to form a compound having the structure:
 EMI5.2
 CgH H0, - .. \ s Ce comf.0 t ', 3-bis (par-hydroxyphenyl) -1-ethyl-cyclohexane.



  Phenol and dicyclopentadiene react to form a bisphenol of general structure:
 EMI5.3
 
The alpha-pinene will be transposed in an acidic medium or at high temperatures to give a diene which will react with the phenol to form a bisphenol of general formula:
 EMI5.4
 

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 where A and G are different and are either a hydrogen atom or a phenyl group.

   More particularly, the reaction product is believed to have the following composition;
 EMI6.1
 
 EMI6.2
 h8ta - Bisph6nol Gamma - Bisphenol (around 65%) (around 35%)
The phenols which can be reacted are hydroxy-arylic compounds comprising a replaceable hydrogen atom attached to a carbon atom of the nucleus in a position which is preferably ortho or para to a phenoli hydroxyl group -   than. Thus the term "phenol" embraces mononuclear hydroxyaryl compounds, and polynuclear compounds, substituted or unsubstituted.

   A "replaceable hydrogen" as this term is used in this disclosure is a hydrogen atom which (1) is attached to an atony of carbon which is not prevented from reacting by spatial arrangement. neighboring atoms which are part of the same molecule, i.e. which do not

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 undergoes no steric hindrance, and (2) does not undergo electronic hindrance, that is to say whose activity is not limited by the presence, in other positions on the phenolic nucleus , substituents tending to attract hydrogen in ortho or para more strongly towards the phenolic nucleus, such as for example nitro groups.

   Among the phenols having replaceable hydrogen atoms attached to the ortho and para positions with respect to the phenolic hydroxyl, some of those deserving special mention are: hydroxybenzenes such as for example phenol, catechol, pyrogallol, resorcinol) phoro-glucinl, and asymmetric trihydroxy-benzene;

   substituted phenols having at the meta positions, the ortho positions or the para position, provided that at least one of the ortho positions or the para position does not have a substituent, one or more substituents leading to the ortho or para such as alkyl groups, aryl groups, alkaryl groups, aralkyl groups, halogens, namely fluorine, chlorine, bromine or iodine atoms, alooxy groups and aryloxy groups. Preferred as dyestuffs attached in the above compounds are straight or branched chain alkyl and aralkyl groups having
1 to 10 carbon atoms,

   in particular lower alkyl substituents, i.e. those having 1 to
6 carbon atoms. Among the substituted phenols, those deserving of special mention are:
 EMI7.1
 

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 cresols, xylenols, gaiacol, 4-ethyl-resorcinol, 4-methylresorcinol, 4-propylresorcinol, carvacrol, methylphenol, ethylphenol, butylphenol, octylphenol, dodecylphenol, eicosylphenol, tricontylphenol and tetracontylphenol, 2,3-dimethylphenol, 2-ethyl-4-methyl-
 EMI8.1
 phenol, 2,4-diethylphenol, 2-methyl-4-bu-byl-phenol, 2-ethyl-5-methylphenol, 2-methyl-5-isopropylphenol,

   2-propyl-5-methylphenol, 2-isopropyl-5-methylphenol, 2,6-dimethylphenol, 2-. methyl-6-ethylphenol, 2,6-diethylphenol, 2-methyl-6-propylphenol, 3,4-dimethylphenol, 3-me-
 EMI8.2
 thyl-4-ethyl-phenol, 3) 5-dimethylphenol) 3.5-diethylphenol, 2-chloro-4-methy? -phenol, 2-ethyl-4-chlorophenol, 3-chloro-4-methylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4-di-
 EMI8.3
 za, ethyl-5-bthylphbnol, 2-ethyl - +, 5-dimethylphenol, 2,4-dietlyl-5-methylphenol, 3,4,5-trimethylphéwnol and higher alkyl phenols.



   Thus the bisphenols of the present invention comprise compounds corresponding to the general formula
 EMI8.4
 where E is the saturated residue of a cyclic organic compound having unconjugated double bonds, each R is independently of each other a hydrogen atom or a hydrocarbon substituent free of unsaturation aliphatic, a halogen atom or a substitute

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 saturated oxyhydrocarbon killer attached to a carbon atom of the phenolic nucleus, this substituent being for example an alkyl, aryl, alkaryl, aralkyl, alkoxy or a fluorine atom: of chlorine, of bromine or of iodine; and "n" is an integer of 1 to 3. Therefore, the term "phenyl" herein embraces substituted phenyl radicals.

   The point of attachment of the above phenolic moieties may be ortho or para, to a phenolic hydroxyl group.



   Therefore, the term "1,4-dimethylene-cyclohexane bisphenol" as used herein encompasses compounds having the formula:
 EMI9.1
   where R and "n" have the meaning defined above; the term "vinylocyclohexane bisphenol" as used herein encompasses compounds having the formula
 EMI9.2
 where R and "n" are as defined above; the term "dioyclopentadiene bisphenol" as used herein,

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 includes compounds having the formula t
 EMI10.1
 beta bisphenol gamma bisphenol where R and "n" have the meaning defined above.



   The new bisphenols can be made by slowly adding the cyclic reagent to a mixture of catalyst and phenol until a stoichiometric ratio of phenol to cyclic reagent is reached.



   It is preferred, however, to use a large molar excess of phenol. Thus, mol ratios of 3 to 20 moles of phenol per mole of cyclic reagent are entirely suitable. Molar ratios of 6 to 12 moles of phenol per mole of ring reagent provide good reaction rates and are easy to handle, and therefore these ratios are preferred. The molar ratio of 10 moles of phenol to 1 mole of cyclic compound provides the optimum rates and, therefore, is especially preferred.



   The reaction can be carried out at a pressure equal to, less than or greater than atmosphere and at temperatures between 30 C and 150 C. Reaction temperatures above 50 C provide good viscosity in the reaction mixture, and temperature

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 res less than 125 C allow the implementation of. reaction without the need for complicated pressure-holding equipment; these temperatures are therefore preferred. Particularly preferred is the reaction under atmospheric pressure at temperatures between 70 C and 100 C.



   The acidic alkylation catalyst used in the present invention comprises a Friedel-Crafts catalyst, comprising the hydrogen (H +) or acid form of a cation exchange resin, i.e. an "acid" resin exchange resin. cations. These resins are insoluble in the reaction mixture and, therefore, there is no problem of separating the catalyst from the effluent from the reaction zone, nor the need to remove small amounts of impurities. in the product. During the entire reaction time and product recovery time, catalyst remains in the reaction zone.



  The service life of the acidic cation exchange resin in this process is almost infinite and, therefore, the resin does not require regeneration, if care is taken to avoid the introduction of metal ions. such as sodium, potassium, calcium, etc. ions or the introduction of other impurities which inactivate the cation exchange groups of the resin. The use of this insoluble catalyst confers the additional advantages of (1) eliminating the need for equipment resistant to acid corrosion, equipment which would otherwise be essential and (2) eliminating all stages of neutralization.

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   Cation exchange resins are substantially insoluble polymeric backbones to which acidic cation exchange groups are chemically attached. The exchange power of the acid groups thus bound and the number of such groups which are available for contact with the reaction mixture determine the alkylation efficiency of a particular cation exchange resin. Thus, although the number of acid groups attached to the polymer backbone of the resin determines the theoretical "exchange capacity", a more precise criterion of the efficiency or catalytic yield is the number of acid groups available for contact with them. reagents.

   This contact can occur on the surface or within the cation exchange resin, therefore, a form of resin which provides a maximum amount of surface area for contact and diffusion, for example microspheres or porous beads. , is highly desirable and this form gives the greatest reaction rate, and the greatest reaction economy in this process. The particular physical form of the cation exchange resin used is not, however, fundamental.



   The cation exchange resins should be substantially insoluble in the actual mixture and in any solvent to which the resin may be serviced. The insolubility of reino is usually attributable to crosslinking within the resin, but it may be due to other factors, for example high molecular weight or high degree of crystallinity.

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In general, the greater the exchange capacity of a resin, that is, the greater the number of milliequivalents of acid per gram of dry resin, the more attractive the resin. Resins with an exchange capacity greater than
 EMI13.1
 about two milliequivalents of acid per gram of dry resin is preferred.

   Particularly preferred are resins to which are attached cation exchange groups derived from acids with very high exchange power. The results obtained with option exchange resins to which sulfonic groups are attached have been highly satisfactory. Among the cation exchange resins which deserve special mention, there are
 EMI13.2
 sulfonated styrene-divinylbenzene copolymers, crosslinked and sulfonated styrene polymers, phônolformaldehyde-sulfonic acid resins, bonzënefocmr7 acid resins: dhyde-sulon.que, eto.

   Most of these resins and many more are commercially available under brands such as Sunberlite XE-100 "(Rohm and Haas Cl) Dowox 50-.wol4" (Dow Chomical 00.) "Permutit Q (mutit 00,); and "Chompro 0-20" (Chemioal Proceosi Co.).



  Many cation exchange resins are received from the manufacturer as the sodium salt or other salt, and they must be converted to acid hydrogen form before serving in the pre-process. The conversion can be easily carried out by washing the resin with a solution of a suitable mineral acid, for example sulfuric acid, hydrofluoric acid or hydrochloric acid.

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  For example, a sulfonated resin can suitably be washed with a sulfuric acid solution.



  The salts formed during the processing operation are conveniently removed by washing the resin with water or with a solvent for the salt.



   It often happens, as a result of one or other of the above washing operations) or as a result of the packaging and shipping method adopted by the manufacturer, that the resin will contain from 50% to 100% of its own weight in water. Preferably, all of this water, except about 2% as a maximum, is removed before using the cation exchange resin.

   Suitable methods for removing water in the resin include drying the resin under reduced pressure in an oven; immersing the resin in molten anhydrous phenol for a period of time sufficient to fill the interstices of the resin with phenol; and an azeotropic distillation of water and phenol in the presence of an excess of phenol.,
Once the resin is "conditioned" in this way to ensure an anhydrous state, that is, less than 2% water in all of the resin, the resin does not require any further reconditioning at any time. moment 'during its use.

   Alternatively, the resin can be conditioned after installation in the process equipment simply by circulating the reaction mixture through the resin until sufficient water is removed. In the latter mode of operation, the dehydration is carried out with phenol.



   The bisphenols of the present invention are easily separable by filtration from the resin.

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 catalyst and can be purified by a vacuum distillation operation which removes unwanted impurities.
 EMI15.1
 



  The Friedel-Crait catalysts used in the present invention can also be halides such as s, .AlOl 31 A1Br:;, Bp3e ZUC'2e FeC13 'Snal4e Ti014' Ticl BoCl2) HfC14 'Thcl ,, Nboi 5e Ta015' U014 ' WC16, SbOl 5) BiC15, AsF3 and ObOI51 oxides such as A120 3P Teo 3 $ p205 etc, salts of phenols) such as titanium, copper, zinc and aluminum phenates;

   mineral acids or salts
 EMI15.2
 acids such as for example HF, H, B02F2 'H; BO2' EµP04 'H3B03' Hale H2So4e and their salts, for example AgS04 'HgSO, and organic acids, for example oxalic acid, para-toluene acid --su.fon.que, acetic acid plus HaSO4 'etc., and aluminosi * - lioates, amorphous or crystalline, synthetic or na-
 EMI15.3
 Turels, such as "Linde" molecular sieves or decation zeolites. These catalysts should preferably be used in amounts of about 1 to about 2 parts by weight per 100 parts by weight of the reaction mixture. Larger or smaller amounts can also be used, for example from 0.55 to 25 parts by weight per 100 parts by weight of the reaction mixture.

   It is preferred that these catalysts are substantially free of water, that is, they contain less than about 2% by weight of water.



   The Applicant has found that from the bisphenols of the present invention, it is possible to synthesize condensation polymers which exhibit,

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 in addition to other interesting physical properties, high glass transition temperatures, high tensile strengths and high tensile moduli.



   For example, polycarbonates of bisphenols can be readily made in interfactial condensation systems. In a polycarbonate synthesis, the bisphenol dichloroformate is first produced with phosgene and dimethylaniline. By polymerization with an aqueous mixture of sodium hydroxide-methylene chloride, a polycarbonate represented by the following structure is obtained.
 EMI16.1
 where E is the saturated residue of a cyclic organic compound having closed unconjugated double bonds; each R is, independently of one another, a hydrogen atom or a hydrocarbon radical free from aliphatic unsaturation; or a saturated oxyhydrocarbon group; "n" is an integer of 1 to 3;

   and "x" is an integer large enough to result in a normally solid polymer.



   As is known in the art, the preferred method of direct phosgenation of bisphenol in an anhydrous or interfacial system can be used on an industrial scale to obtain the polyoarbonate.

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   Alternatively, the bis-phenol can be copolymerized with other known bisphenolas such as bis-phenol A. The structure of such copolymers can be represented as:
 EMI17.1
 where E, R and "n" are as defined above; D is
 EMI17.2
 a divalent radical such as an alkylidene or cy- eloalkylidene arylene radical, O 0 0
 EMI17.3
 ..0-, -0-, -S-, -8- and ...-; and "x" '. t "y" are numbers
O integers large enough to be normally solid polymers.



   Polyurethanes can also be made from
 EMI17.4
 from bisphenolsq Thus, the .dichlorof; ormiate of bisphenol will react with, for example, piperazino to form a polyurethane of structure
 EMI17.5
 where E, R and "n" and "x" have a meaning defined above,
Other synthetic solutions, such as direct phosgenation or ester group exchange, can also be used to make polyurethanes.



   The synthesis of polyesters of bisphenols can be carried out by reacting dicarbo- acids

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 xyls, esters or acid halides with bisphenols, with or without the use of a solvent.
 EMI18.1
 Poly (hydroxyethore) bisphenols can be made. by the procedure described in French Patent No. 1,309,491 of November 2, 1961.



   As other applications of bisphenols, there is their use as a curing agent for epoxy resins, as bactericides) fungicides,
 EMI18.2
 miticides and anti-oxidants,
Non-limiting Examples 1 to 14 below illustrate the manufacture of bisphenols, while Examples 15 to 19 illustrate, without limitation) the new polymers produced in par. shot of these bisphenols.
 EMI18.3
 : E3 # MPLE Manufacture of 1 4-dimetin bisphenol c: vclohexl3I
188 g are introduced into a three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer) a reflux condenser) an ampoule and a heating jacket.

   (2 moles) of freshly distilled molten phenol and 125 g (about 0.5 equivalent of hydrogen) of the acid form of "Dowex '
 EMI18.4
 50 L-4 "(styrene .-. Diviuylbenzno sulfonic copolymer) in which almost all of the water has been displaced by the phenol. The resulting suspension is heated to 70-75 C and the heating is then stopped. We add
 EMI18.5
 then 22 g (0.2 mole) of 1) 4-dimethylene cyclohexana, drop by drop, while adjusting the heat release using cooling water in order to maintain the temperature at 70-75 C. When the heat release decreases) heating is applied. At the end

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 After 22 hours of the reaction period, the mixture is filtered and the catalyst washed with 250 ml of freshly distilled molten phenol.

   The filtrate and the washings are combined, they are distilled to remove the fraction boiling up to 200 C at 1mm-10mm. The amount of crude 1,4-dimethylene cyclohexane bisphenol remaining in the pot; of distillation as a residue is 55 g, scit a yield of 90% by
 EMI19.1
 based on the weight of the 1,4-dimethylene-cyclohexane introduced. A sample recrystallized from toluene
 EMI19.2
 for analysis has a melting point of 195 ° C., a hydroxyl number of 11.34% (theoretical value: 11.49%) and a molecular weight of 290 (theoretical value:: 296).



   The infrared spectrum of the crystalline product obtained from toluene shows an intense band at 12 microns indicating a para-alkylphenol. The nucleus magnetic resonance spectra of this crystalline product verifies by counting the relative number of aromatic and aliphatic hydrogen atoms that it is the product of 2 moles of phenol and 1 mole.
 EMI19.3
 of diti6thylène-cyclohoxane) and that it is indeed a true bisphenol.

   The magnetic resonance spectrum of the nucleus also suggests that this product is a mixture (approximately 1: 1) of 2 isomers, namely
 EMI19.4
 1) 4-dimethyl-1) 2-bis- (p-hydroxyphenyl) cyolohexane and 1, 4-.dimethyl-1, 3..bia (p-hydroxyphenyl) eyclohe .. xane. This finding is confirmed by thin layer chromatography which reveals. also the presence of other isomers of bisphenols in the mother liquor toluoniquo after removal of crystalline isomers.

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   The amount of cation exchange resin can vary over a wide range with corresponding reaction rates. Catalyst concentrations of between about 0.1 and up to 50% are preferred.
 EMI20.1
 about 5 equivalents of acid per mole of 1,4-dimethyl-15n.e-cyc.ohExzano duo. Lower concentrations provide slower reaction rates.
 EMI20.2
 Resin concentrations of cationic resin ranging from about 0.3 equivalents of acid and
 EMI20.3
 About 4 equivalents of acid per mole of 1,4.-dimethylenecyolohexane have given excellent results and are particularly preferred.



   A concentration of about 1 equivalent of acid per mole of 1,4-dimethylene-cyclohexano provides the optimum combination of reaction speed, noise and product quality. It is a conoon-
 EMI20.4
 Particularly desirable traction when operating at temperatures between 7 ° C and 75 ° 0 with a ratio of 1: 1 between phenol and 1,4-dim6ethylanocyclohexane.



     EXAMPLE 2
 EMI20.5
 F>: r3.axtion dūbis (ortho-cresol) do 1 ... dirabt .énc.- ç:?: (\ L ohox, m1s
1.080 g (10 moles) of ortho-cresol ot 250 are introduced into a three-necked round-bottomed flask fitted with a stirrer, a thermometer, a reflow condenser and a funnel with a stopcock. g (about equiva-
 EMI20.6
 slow acid) of a csahangauao resin of cations which have a sulfonated styrene-divinyl benzene copolymbre prepared6o coinmo described above by replacement) using or- tho-cresol, almost all of the water, a ost-àd3, ro up to a water content of less than 2%.

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   The mixture of catalyst and gold is heated. tho-cresol to 70 -75 ° C and 108 g is added dropwise over a 30 minute period. (mole)
 EMI21.1
 1,4-imethylene-cyolohexano. By cooling during this period, the temperature of the reagent is maintained between 700 ° and 75 ° C. After the addition and when the evolution of heat has subsided, heating is applied for an additional 5 hours to maintain a temperature between 70 and 75006
After this time, the hot reaction mixture is filtered and the catalyst washed with 250 g of molten ortho-cresol.

   The filtrate and the washings are combined, distilled at reduced pressure to a final residue temperature of 200 ° C. at a pressure of about 1 mm Hg. The residue includes
 EMI21.2
 bis- (ortho-cresol) do 1,4-dimethyleno-oyolohoxano.



  EXELE .3: a "ar.crxt.an du bïs.ortho-ohloroph6nol da 1¯, 4-d, mb¯ thyl & no-oyc1ohexonQ
The apparatus and procedure of Example 2 are used but the ortho-cresol is replaced by gold
 EMI21.3
 tho-chlorophonol. The residue comprises the bis- (ortho-chlorophenol) of 1 4..dïrtlayrōcyclohoxanQ Other hydroxy "aryliquos compounds can be reacted with 1, 4-d.mthylns¯cyc, ohoxano to produce the corresponding compounds. .

   For example, we make D..1: I6mont react doo hydroxyaryl compounds polyf nuc16airos, nub ± titu6S or unsubstituted, for example naphthols ot in particular los alpha- and beta ...
 EMI21.4
 naphthols with 1) 4-dimethyleno-oyolohexano using as catalysts the carbon exchange resins.

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 like this inventions
The production is illustrated by the following example
 EMI22.1
 EX'.Iril'hE 4 Manufacture of b3.s al ha-ne. 1,4-Dimethylen-C118 htol; x120. "
900 g of alpha-naphthol are placed in a 2 liter flask fitted with a stirrer, a thermometer, a stopcock and a reflux condenser.

   The temperature is brought to 100 ° C. and, while stirring, 200 g are added. of 6changouso resin of ca-
 EMI22.2
 tions ("Dowox 50 X-4") oven-dried (105 110 C) under acidic in foruie (e)
Stirring is continued and added dropwise over a period of one hour at 100-105 C 54 g of
 EMI22.3
 1, 4-d3: nthy7.âLo-ayclohoxanc. Heating and stirring are continued for 4 hours after the addition is complete.
 EMI22.4
 



  The rGactioru.E1 mixture is filtered and the cationic chancouso resin washed with 200 g of alpha-mphtol. Filter 10 and the wash liquors and 7 .; distillate at a pressure lower than 0.5 plti of ftiercure up to a final residue temperature of 200 C.



     The residue is 1,4-di- bis (2-naphthal)
 EMI22.5
 methylenc-cyclohexano.



  EXAMPLE 5 Manufacture of vinyl-cyclohexene iErph6nol.



   The equipment used is a three-necked round-bottomed flask fitted with a stirrer, a thermometer, a rc-.flux condenser and a stopcock. We

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 add 940 g (10 molos) of fresh phenol to the flask
 EMI23.1
 sweet distilla and 250 g. (approximately 1 equivalent of aoido) of a 4% sulfonated styrene copolymer of divinylbonzeno, 6 ohm cationic resin which was prepared according to the above described above by replacing with phenol of the quasi all of the water, that is to say,
 EMI23.2
 has a water content of less than 2%.



  The mixture of catalyst and phenol is heated to 70-75 ° C. and 108 g (1 mole) of vinyl is added dropwise over a period of 30 minutes.
 EMI23.3
 ayolohoxene. By cooling during cotto prioao) the temperature of the reagent is maintained between 70 ot 75 0.



  After the addition and once the dE5D.e; Olllont duo heat} a heating is applied for 5 additional hours to maintain a temperature ooTa taken between 70 and 75 C
After this period) the mixture is filtered.
 EMI23.4
 Hot C3 ru: 10 1 and the catalyst is washed with 250% molten halol. The filtrate and the washings are grouped together and distilled at reduced pressure to a final residue temperature of 200 ° C. to the pressure of about 1 mm of mercury.



   Lo raw residue, light amber in color from
 EMI23.5
 bisphenol do vinyl-cyolohexene peso 193 g is an en-. of the calculated 70% n bisphqnol, and with respect to viuyi-oyclohcxèno.



   This crude residue is crystallized from an equal weight of hot toluene, and this produces 100 g of fine white crystals having a melting point, not
 EMI23.6
 corrected, from 183 -184 Q * The percentage of hydroxyl group, determined for the crystalline product, is

 <Desc / Clms Page number 24>

   11.50 - 0.03%;

   the theoretical value calculated for the
 EMI24.1
 vinyl-cyclohexene bisphenol is equal to 11.48%. the product of the example above is proved to be 1,3-bis (para-hydroxyphenyl) -1-ethylcy-
 EMI24.2
 clohexan.e by a comparison of the analysis élémontain0, and d.es infrared spectra and .nagnetic resonance. that of a core of a hydrocarbon, 1,3..diphnyl..1-ethylcyclohexane, prepared at from this product by selective removal of its phónolic hydrbxyl groups under controlled conditions by reducing cleavage of a phosphoric ester of phenol, as described by: DW Kenner & NR, Williams) J. Chem. Soc. 1955,522.
 EMI24.3
 



  The synthesis of the known 1,3-diphny-1-ethyl-cyclohexanc is carried out as follows. 3, 5-diX 'is prepared. nyl-6-c s, rbothoxycy elohaxene-2-oilo-1 (A) by an aldolïquo condensation of ethyl acetoacetate with benzalac6tophénono, condensation catalyzed by sodium ethylatc. The melting point do (A) corresponds to that indicated by E. Knoovonagol, E. Spoyor, Bort, 35 (1902). The hydrolytic decarboxylation of do (A) for .ob-
 EMI24.4
 Hold the µ, 5-aiphenylcyclohoxeno-2-ono-1 (B) using an aqueous sodium hydroxide solution at reflux.

   The melting point of (B) corresponds to that
 EMI24.5
 given by E. Knoevcnagel, A. Erler, Ber. 36th 2133 (1903) and W. Dicckmann, K.V. Fischer, Ber., 44, 971 (1911).



  Compound (B) is reacted with ethylmagnesium bromide to produce 3,5-diphenyl-3-ethylcyclohexanone (0). The structure of (C) is confirmed by analy.-
 EMI24.6
 elementary se, infra-red specter and resonance spectrum: nuclei wsnetics. By uno reduction do lYolff-

 <Desc / Clms Page number 25>

   Kisher of (C), 1,3-diphenyl-1-ethylcyclohexane is produced which is characterized by elementary analysis and infrared and magnetic resonance spectra of the nucleus.



   The infrared spectra of the synthetic 1,3-dipheny1-1-ethylcyclohexane, and of the parent hydrocarbon of the product of Example 1 were identical.



  The magnetic resonance spectra of the nuclei were identical except for a peak at 78 cycles per second (alkane hydrogen region) in the synthetic compound, which peak was attributable to an impurity present in the sample. Mixtures of the soft materials, analyzed on two different types of gas chromatography columns, showed only one main peak.



   EXAMPLE 6 Manufacture of vinyl-cyclohexene bis (ortho-cresol)
250 g are introduced into a tri @ ol round-bottom flask fitted with a stirrer, a thermometer, a reflux condenser and a tap ampoule. (approx. 1 acid equivalent) of a 4% sulfonated styrene copolymer of divinyl benzene, cation exchange resin prepared as described above by replacement with ortho-cresol of almost all of the water contained, that is to say up to a water content of less than 2%.



   The mixture of catalyst and ortho-cresol is heated to 70-75 ° C. and 108 g (1 mole) of vinylcyclohexene are added dropwise over a period of 30 minutes. By cooling during this period, the temperature of the reagents is maintained between 70 and

 <Desc / Clms Page number 26>

 75 C. After the addition and when heat is released) heat is applied for an additional 5 hours to maintain a temperature between 70 and 75 C.



   After this time, the hot reaction mixture is filtered and the catalyst washed with 250 g of molten ortho-cresol. Or group the filtrate and the washing liquids, they are distilled at reduced pressure.
 EMI26.1
 up to a final residue temperature of 200 C at a pressure of about 1 mm Hg. The residue con-
 EMI26.2
 takes 10 bis-or4sol of 4-vinyl-cyclohexeno, i.e. 1,3-bis (ortho-Nethyl-para-hydroxy-phenyl) -1-6yloyclohoxane.



  EXAMPLE 7 Manufacture of bis (ort40-chlorophlnol) do vinyl-cYC7.ō hexene
The apparatus and the operating procedure are used.
 EMI26.3
 Example z But ortho-or6sol is replaced by ortho "'ohlorophúnol. The residue coi2l) renders the bis-chlorophenol of 1 + -vuiyl-cyclohexene, that is to say 1,3-bis (ortho-chloro-para-hydrucyphenyl) -1-b thrlcyc loYexana.



  EXE? '31 <E 8 Manufacture of vinyl-cyclohexene bis (2-na2htol)
900 g of alpha-naphthol are placed in a 2-liter flask fitted with a stirrer, a thermometer, a stopcock and a reflux condenser. The temperature is brought to 100 ° C. and 20U g of cation exchange resin are added while stirring.
 EMI26.4
 ("Dowex 50 4", oven dried (105 -110 0)) in the acid form (H +).



   Continue stirring and add drop

 <Desc / Clms Page number 27>

 drip in. a period of one hour at 100-105 C 54 g of 4-vinyl-cyclohexèno. Heating and stirring are continued for 4 hours after the addition is complete.



   The reaction mixture is filtered and the cation exchange resin with 200 g of alpha-naphthol is washed. The filtrate and wash liquors are combined and distilled at a pressure below 0.5 mm Hg to a final residue temperature of 200 ° C.



   The residue is 4-vinyl-cyclohexene bis-naphthol.



    EXAMPLE 9 Manufacture of dicyclopentadiene bisphenol
In a round-bottomed three-necked flask of 1 liter, equipped with a mechanical stirrer) a thermometer) a reflux condenser, a stopcock and a heating jacket, are placed 940 g (10 moles ). of freshly distilled molten enol and 250 g (approx.
1 equivalent of hydrogen) of the acid form of "Dowex
50 X-4 "of which almost all of the water has been displaced by phenol. The resulting suspension is heated to 70-75 ° C. and the heating is then stopped. 1 mole is added dropwise. of dicyclopentadiene (132 g) however the heat release is controlled with cooling water to maintain the temperature at 70 -75 C.

   When the heat release decreases, heating is applied. After the 22 hour reaction period, the mixture is filtered and the catalyst washed with 250 ml of freshly distilled molten phenol. The filtrate is grouped together and the li-

 <Desc / Clms Page number 28>

 queurs do lavago and distilled to remove the fraction boiling up to 200 C at a pressure of 1 to 5 mm. The amount of crude dicyclopentadiene bisphenol remaining in the still as a residue in the still was 312 g, yielding 97.5%.



  A sample, recrystallized from toluene for analysis, has a melting point of 198-200 ° C, and a hydroxyl number of 10.4% (theoretical value 10.6%).



   Analysis by means of chromatography on reverse phase filter paper, in which the sample is carried by an aqueous alkaline solution through the paper impregnated with tri-cryesyl phosphato, indicates that the product is essentially bisphé. dicyclopentadiene nol.

   There is a single intense band with an edge ratio (Rf) value of 0.14 and a very weak band with a value of 0.07,
Cyclopentadiene bisphenol dimethyl ether was prepared as a further proof of structure by heating under reflux a solution of 4.4 g (0.014 mole) of dicyclopentadiene bisphenol in 50 ml of acetone with 1.2 g (0.03. mole) of sodium hydroxide pellets and 4.0 g (0.03 mole) of methyl iodide for 3 hours. This mixture is heated under reflux for a further 4 hours with an additional 4.0 g of methyl iodide.

   On cooling, a crystalline product separates with a yield of 90% and this product has a melting point. from 87 to 89 C after recrystallization from iaopropanol. The product is further identified by the infrared absorption spectrum as dicyclopentadiene bisphenol dimethyl ether.

 <Desc / Clms Page number 29>

 



   The amount of cation exchange resin used can vary over a wide range with corresponding reaction rates. Catalyst concentrations of between about 0.1 and about 5 equivalents of acid per mole of dicyclopontadiene are preferred. Lower concentrations provide slower reaction rates. Concentrations
 EMI29.1
 Cation-exchanged resin of from about 0.3 equivalents of an acid to about 4 equivalents of acid per mole of dicyclopontadieno have given excellent results and are particularly preferred.



  A concentration of about 1 equivalent of 4chanL7, c., Åsr- resin acid, cations per mole of dicyclopentadiene provides the optimum combination of rate of release.
 EMI29.2
 reaction, slow r0nde and product quality. This is a particularly desirable concentration when operating at temperatures between about 70
 EMI29.3
 and 7500, with a ratio of 10:

  .i Miter phenol and di-cyclopentadiôno, EX ± 1 '± PLE 10 Manufacture of bis (ortlio-cresol) .do dicyclol2entadiene In a three-necked round-bottomed flask, fitted with a stirrer, a thermometer) of a reflux condenser and a stopcock, add 1.080 g (10 molos)
 EMI29.4
 of ortho-cresol to 250 g (approximately 1 equivalent of acid) of a sulfonated styrcne-divinyl benzine copolymer, cation exchange resin prepared as described above by replacing with ortho-cresol the quasi- all of the water was present, that is to say up to a water content of less than 2%.



   The mixture of catalyst and ortho-

 <Desc / Clms Page number 30>

 cresol to 70 -75 ° C. and 132 g (1 mole) of dicyclopentadiene are added dropwise over a period of 30 minutes. Cooling during this period maintains the temperature of the reagents between 70 and 75 C. After the addition, and once the evolution of heat has calmed, heating is applied for an additional 5 hours to maintain a temperature between 70 and 75 C. .



   After this period) the hot reaction mixture is filtered and the catalyst washed with 250 g of molten ortho-cresol. The filtrate and washings are combined and distilled at reduced pressure to a final residue temperature of 200 ° C. at a pressure of about 1 mm Hg. The residue comprises bis- (ortho-cresol) dicyclopentadiene.
 EMI30.1
 

 <Desc / Clms Page number 31>

 



    EXAMPLE 11
 EMI31.1
 Manufacture of bis, ortho-ch7.orohnol d diçyoloen. tadiene
The apparatus and procedure of Example 2 are used, but ortho-cresol is replaced by ortho-
 EMI31.2
 chlorophenol. The residue comprises the b.s- (oxtho.chlorophenol) of dioyclopentadiene.



   Other hydroxy compounds can be reacted
 EMI31.3
 aryliquos with dicyclopontadien to produce the corresponding bis-compounds. For example, substituted or unsubstituted polynuclear hydroxyaryl compounds, for example naphthols and in particular alpha- and beta-naphthols, are readily reacted with.
 EMI31.4
 dicye7.opentadiene using the cation exchange resins of the present invention as catalysts.



   The manufacture is illustrated by the following example: EXAMPLE 12
 EMI31.5
 Fab? '\ 9.6, j.on d. \ N.aIJhtol de.! Ii.oy¯c) .. Q.J2 ..! L: ac1me.



  In a 2-liter flask, fitted with a stirred ur; them., A thermometer, a tap EYampo1.1.1e and a reflux condenser, 900 alpha-naph% ol. The temperature is brought to 100 ° C. and 200 g of cation exchange resin ["Dowex 50 X
 EMI31.6
 4 ", dried in an oven (105 -110 7 in the acid form (H +).



   Continue stirring and add drop
 EMI31.7
 100 -105 0 66 of dicyclopentadibne was removed in a period of one hour. One continues heating and stirring for 4 hours after completion of the addition.
 EMI31.8
 The reaction mixture is filtered and the

 <Desc / Clms Page number 32>

 the cation exchange resin with 200 e; alpha-naphthol. The filtrate and the washings are combined and distilled at a pressure of less than 0.5 mm Hg to a final residue temperature of 200 C.



   The residue is dicyclopentadiene bis-naphthol.



   EXAMPLE 13 Manufacture of alpha-pinene bis-bhenol
In a 1 liter three-necked flask, equipped with a mechanical stirrer, a thermometer, a heating jacket, a reflux column and a stopcock, 470 g (5 moles) of phenol are added. freshly distilled and 250 g (about 1 equivalent of hydrogen or acid) of an exchange resin;. sulfonated styrene-divinyl benzene copolymer ions ("Dowex 50 X 4"), resin which was prepared by replacement with Using phenol almost all of the catalyst water in the acid form.



   The mixture of phenol and catalyst is heated to 70 -75 C, and 68.0 g (1/2 mole) of alpha-pinene is added dropwise over 15 to 30 minutes. at a rate capable of maintaining, thanks to the chorus release, a temperature of 70 to 75 C. Once the release of heat has subsided, heating is applied to maintain 70 -75 C for an additional 5 hours.



   At the end of this period, the reaction mixture is filtered hot in order to remove the catalyst. The catalyst is washed with about 250 g of phenol. We group

 <Desc / Clms Page number 33>

 eg the filtrate and the washing liquors and then distilled at reduced pressure to a temperature
 EMI33.1
 final in the Xe 20000 distillation pot at the pressure of about 1 to 5 cita of mercury.



   The light amber colored residue weighs 140 grams, a yield of 86.5 based on alpha-pinene, and calculated as bisphenol. Crystallization of this crude product from about twice its weight of toluene gives 70 g of snow-white crystalline product (melting point: 90-105 ° C).
50% of the crude product, ie a yield of approximately 44% relative to the initial alpha-pinene. The hydroxyl content of this product is 10.47% (theo-
 EMI33.2
 risk 10.5 5).



  1JY.:3IPLE 14, iL9: .P.rl: .9A.t.ion. du ..9.i, s Benol from alphf!: 'p.i
Example 13 is repeated except that the reaction is carried out in a column packed with the exchanging resin.
 EMI33.3
 Ionizer at Q5 -90 C with a catalyst contact time of 45 minutes, The yield of crude product is
 EMI33.4
 of 70 'o. The amount of crystalline product is 70% of the crude product, or 49 relative to ltalpha-pinère.



   The product of Example 1 is identified by gas chromatography and nuclei magnetic resonance techniques.
The product of Example 1 is methylated by reaction with methyl iodide in acetone under reflux in the presence of sodium hydroxide.



   The dimethyl ether of the product of Example 1 is fractionated by gas chromatography into 2 cons-

 <Desc / Clms Page number 34>

 tenants. The premoer, constituting about 65% of the product, is dimethyl ether of a compound referred to herein;

   as being beta-bisphenol, and the second component, constituting approximately 35% of the product, is dimethyl ether of a compound referred to herein as gamma-bisphenol,
Referring to Figure 1, which shows the magnetic resonance spectrum of the nuclei of the major constituent, beta-bisphenol, it is seen that the complex absorption at 4 cycles per second indicates the presence of an isopropyl group. , and absorption at 79 cycles per second indicates a methyl group of benzyl radical.

   Among the possible isomers of a bisphenol made from one mole of alpha-pinene and two moles of phenol, only the following compounds contain both an isopropyl group and a methyl group of benzyl radical.
 EMI34.1
 

 <Desc / Clms Page number 35>

 
 EMI35.1
 



   Note that the difference between the isomers is that the phenyl groups are ortho, meta or para to each other. The methyl group of radio.:.;, Benzyl is shifted 10 cycles per second to the lower fields compared to the similar group
 EMI35.2
 observed in the spectrum of alpha-bisphenol, the structure of which was presented above. It can therefore be concluded that the correct structure is that of the isomer in which the methyl group of the benzyl radical will form.
 EMI35.3
 temee3 feels the presence of the neighboring paxa-hydroxyphenyl group, i.e. structure I.

   In structures such as II and III, such an effect would be mitigated if it were even present. The infra-red spectrum of beta-bisphenol indicates a predominance of para substitution.



  The magnetic resonance spectrum of the nuclei (Figure 1) in the region indicating the aryl group (400-450 cycles per second) has two superimposed nibble signals, the lower halves of which show different chemical shifts, indicating a difference in the nibbles. alkyl substituents (eg, tertiary alkyl and secondary alkyl). The quartet group indicates that the hydroxyphenyl groups are para.

   So the

 <Desc / Clms Page number 36>

 - 35 - structure of beta-bisphenol is indicated as (I) or:
 EMI36.1
 
Referring to Figure 2, which shows the magnetic resonance spectrum of the nuclei of the minor constituent, gamma-bisphenol, we can see two equivalent benzyl radical methyl groups (75 cycles per second) and one non-derivative methyl group. of a benzyl radical, the separation of the doublets indicating that @@ is attached to a carbon atom which carries only one hydrogen atom.

   Among the possible isomers of a bis-phenol prepared from one mole of alpha-pinene and two moles of phenol, the following salts have a carbon atom bearing a methyl substituent and bearing only one atom. of hydrogen.
 EMI36.2
 

 <Desc / Clms Page number 37>

 
 EMI37.1
 



   The benzyl-sheathed dimethyl groups show the same chemical shift as those of the alpha-isomer shown above, so structure IV is indicated as the structure of gamma-bisphenol, since the hydroxyphenyl group is therein. the farthest from the geminous dimethyl groups of the benzyl radical. Thus the structure of gamman-bisphenol is indicated as being:
 EMI37.2
 
All parts and percentages given herein are by weight.



     EXAMPLE 15 Manufacture of 1,4-dimethylene cyclohexane bis-phenol dichloroformate,
Has a suspension of 29.6 g (0.1 mole) of 1,4-dimethylene-cyclohexane bisphenol and 250 ml of anhydrous toluone, cooled to 5 C and contained in a

 <Desc / Clms Page number 38>

 Three-necked round-bottomed flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and a funnel, 19.8 g (0.2 mol) of phosgene are added. A solution of 24.2 (0.2%) of M, N-dimethylaniline in 25 ml of anhydrous toluene is then added dropwise from the funnel. The reaction mixture is stirred at room temperature for about 2 hours.

   The insoluble dimethylaniline hydrochloride is separated from the reaction product by filtration, and the filtrate is freed from its solvent by vacuum distillation. The residue is dissolved in 100 ml of methylene chloride and the solution is passed through a column of silica gel (30 cm high and 4.1 cm in diameter). The product is eluted with 600 ml of methylene chloride, the eluates are pooled and the sovant is removed therefrom by distillation. The oily residue is identified by infrared absorption spectra as 1,4-dimethylenecyclohexane bisphenol dichloroformate having an absorption band typical of a chloroformate carbonyl group at about. 5.7 microns.

   There is no absorption at 3.0 microns, the absorption band characterizing the phenolic hydroxyl groups.



   EXAMPLE 16 Polymerization of bisphenol 1,4-dimethylene-cyclohexane dichloroformate
A solution of 4.21 g (0.01 mole) of the bisphenol of 1,4-dimethylenecyclohexane dichloroformate in 50 ml of methylene chloride is added to a solution of 1.0 g of sodium hydroxide. sodium, 50 m1 of water, 3

 <Desc / Clms Page number 39>

   Drip triethylamine and 0.014 g of phenol, contained in a 250 ml knitted Morton flask, fitted with a mechanical stirrer, reflux condenser and
 EMI39.1
 thermometer. The reaction mixture is stirred for 10 minutes. The organic layer is washed with three 200 ml portions each of water with stirring for 10 minutes in the Morton flask.

   The organic layer is washed with a solution of 3 ml of 87% H3PO4 in 100 ml of water while stirring in the Morton flask for 30 minutes. The organic layer is washed with 200 ml portions each of water until the aqueous layer has a pF of approximately 6 at the end of the wash. The organic layer is then poured slowly into a Waring mixer containing 300 ml of isopropanol. So he rushes
 EMI39.2
 a pO.yCLa.xbG lat0 which is washed in the mixer with three portions of 250 ml of water each.

   After drying the product under vacuum, it shows a strong infrared absorption band characterizing carbonyl groups at
 EMI39.3
 '*' **. approximately 5.65 microns and has a reduced viscosity equal to 0.68 when measured at the concentration of 0.2 g of product in 100 ml of chloroform at 25 C. This
 EMI39.4
 polycarbonate of bio1Jhenol of 1,4-dim ± thylone-oyclvhexane thus obtained can be represented by the following structure
 EMI39.5
 where "x" is an integer having sufficiently high values to result in a normally solid polymer.

 <Desc / Clms Page number 40>

 



   Films of this polycarbonate cast from the chloroform solution were used for an Instron machine analysis, which revealed a tensile strength of 490 kg per cm2, a tensile nodule of 16,100 kg per cm2, and an elongation of 17 to 75 %. The glass transition temperature (Tv) is 240 C and the impact resistance per pendulum is equal to 0.75 kgm / cm3.



   EXAMPLE 17 Conolymerization of 1,4-dimethylene-cyclohexane bisphenol with bisphenol A dichloroformite
In the apparatus described in Example 16, a solution of 1.77 g (0.005 mol) of bisphenol-A dichloroformate in 25 ml of methylene chloride, 25 ml of water, 3 drops is stirred. of griethylamine, 0.5 g of sodium hydroxide, 0.01 g of phenol and 1.48 g (0.005 mole) of 1,4-dimethylene-cyclohexane bisphenol. Stirring is continued for 5 minutes and the procedure described in Example 16 is then followed.



  The mixed polycarbonate yield is, after vacuum drying, equal to 90%. This product has a reduced viscosity, in chloroform at 25 ° C., equal to 3.64 (sample of 0.2 g in 100 ml of chloroform). Analysis in the Instron apparatus of films of this polycarbonate cast from chloroform solutions shows a tensile strength of 700 kg per cm2, a tensile modulus of 18,900 kg per cm2, and an elongation of 16 to 120. The glass transition temperature is 205 C, and the impact strength value of the pendulum is 0.84 to 5.04 kgm / cm3.

   The structure of this polycarbonate is shown below:

 <Desc / Clms Page number 41>

 
 EMI41.1
 where "x" and "y" are integers having values high enough that they are normally solid polymers.



   EXAMPLE 18
 EMI41.2
 Manufacture of homopo oolycarbonate, lymer of 1.3-bis- Cnara-hydroxyphn, yl) .. 1 hyl.-celohexane
In a 2-liter glass reactor, fitted with a sealed stirrer, pH electrodes, a thermometer, a gas inlet tube, a valve funnel and a a reflux condenser is introduced;

   
 EMI41.3
 
<tb> Bisphenol <SEP> from <SEP> 4-vinyl <SEP> cyclohexene <SEP> 163 <SEP> g <SEP> (0.55 <SEP> mole)
<tb>
<tb>
<tb>
<tb> Hydroeulfite <SEP> of <SEP> sodium <SEP> (anti-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> oxidizer) <SEP> 0.11 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb> p-Phenylphenol <SEP> (agent <SEP> of <SEP> termi-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> naison <SEP> of <SEP> growth <SEP> of <SEP> string) <SEP> 5.0 <SEP> g <SEP> (0.029 <SEP> mole)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Solution <SEP> of <SEP> sodium <SEP> <SEP> 230.3 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 20.3 <SEP> g <SEP> NaOH
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 210 <SEP> g <SEP> H2O
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> methylene <SEP> <SEP> 718 <SEP> g
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Triethylamine <SEP> (catalyst) <SEP> 1,

  67 <SEP> g
<tb>
 While stirring, phosgene is bubbled through the reaction mixture and simultaneously, a solution of 36.9 g of NaOH in 389 g of water is added dropwise to maintain the pH of the reaction mixture between 10.5

 <Desc / Clms Page number 42>

 and 11.5. After the addition of the sodium hydroxide solution is complete, the addition of phosgen is continued until the pH of the reaction mass has dropped to 7.0. During the entire phosgenation period, the temperature is maintained at 250 t 3 C. A total of 69 g of phosgene * is used. To the reaction mass, a solution of 25 g of NaOH in 50 g of water is then added.

   The reaction mixture is stirred for 10 minutes, allowed to stand until two layers develop, and the aqueous layer is withdrawn. The polymer solution is then stirred with 800 ml of distilled water and the aqueous layer is decanted again.



    , We repeat this operation 4 times. The polymer solution was then stirred for two hours at room temperature with 230 ml of an aqueous solution of hydrochloric acid (4.3% kCl). The acidic aqueous layer was then decanted and the polymer solution washed as above with 800 ml portions each of water until the decanted water layer was free of chloride. The polymer solution is further diluted with 1,600 ml of CH 2 Cl 2, filtered, and coagulated in 3,000 ml of isopropanol (vigorously stirred). The polymer which precipitated was collected by filtration and dried for 72 hours at 100 ° C. in a circulating air oven.

   The final polymer has a reduced viscosity in methylene chloride at 25 ° C. (0.2 g per 100 ml of solution) equal to 0.58. It is completely soluble in methylene chloride, dioxane, tetrahydrofuran and chloroform. The polymer has a melt flow index of 0.15 decigrams per minute at 280 ° C and is thermally stable at 3000 ° C.

 <Desc / Clms Page number 43>

 



   Determinations of the physical and chemical properties were made on a sample of the polymer, here are the results obtained; Sample: molded plate - thickness 0.5 mm molded at 280-300 0 to 140 kg / em2 Results on an "Instron" machine at room temperature
 EMI43.1
 - (speed -4.

   0.5 om / minute)
 EMI43.2
 
<tb> After <SEP> 100 <SEP> After <SEP> 24
<tb>
<tb>
<tb> hours <SEP> to <SEP> 150 0 <SEP> hours <SEP> in
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Light <SEP> to <SEP> air <SEP> H20 <SEP> to <SEP> 100 0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Resistance <SEP> to <SEP> the
<tb>
<tb>
<tb>
<tb>
<tb> traction <SEP> (kg / cm2) <SEP> 543,200 <SEP> 564,2 <SEP> 604,1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Traction <SEP> module <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> (kg / cm2) <SEP> 14490 <SEP> 14490 <SEP> 15610
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Elongation <SEP> (%) <SEP> 8,2 <SEP> 11 <SEP> 7, <SEP> 2 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Shock <SEP> by <SEP> pendulum
<tb>
<tb>
<tb>
<tb>
<tb> (kgm / cm3) <SEP> 1.12 <SEP> 0.73
<tb>
 Impact tensile strength (kgm / em3)
 EMI43.3
 
<tb> 23 C <SEP> 1 <SEP>,

  72
<tb>
<tb>
<tb> 0 C <SEP> 2.62
<tb>
<tb>
<tb>
<tb> - <SEP> 20 <SEP> 2, <SEP> 21 <SEP>
<tb>
<tb>
<tb>
<tb> - <SEP> 40 C, <SEP> 2.06
<tb>
 Electrical properties
 EMI43.4
 10 'cycle 10 cycle
 EMI43.5
 
<tb> Factor <SEP> of <SEP> dissipation <SEP> 0.0013 <SEP> 0.0039
<tb>
<tb> Dielectric <SEP> constant <SEP> 2.85 <SEP> 2.85
<tb>
<tb>
<tb> Arc resistance <SEP> <SEP> (sec.) <SEP> 123
<tb>
<tb>
<tb> Chemical <SEP> resistance
<tb>
   (Weight increase after a week of immersion at room temperature)

 <Desc / Clms Page number 44>

 
 EMI44.1
 
<tb> Variation <SEP> ion¯ <SEP> of <SEP> weight <SEP> (%)
<tb>
<tb> 10 <SEP>% <SEP> NH4OH <SEP> No <SEP> of <SEP> change
<tb>
<tb> 10 <SEP>% <SEP> NaOH <SEP> Negligible
<tb>
<tb> 30 <SEP>% <SEP> HSO <SEP> Plus <SEP> 0,

  66
<tb>
<tb> Acetone <SEP> Plus-20
<tb>
<tb> Toluene <SEP> Disaggregated
<tb>
 
 EMI44.2
 Trichloroet # y1éÀe. Disaggregated
 EMI44.3
 
<tb> H20 <SEP> -0.25
<tb>
 
 EMI44.4
 95 5 '{ethanol (aq.) Plus 1', 4 Resistance to stress cracking *. (24 hours at temperature T) E = 0.73% at 13 C (Test carried out with parabolic test assemblies
 EMI44.5
 as described in "TheCrazing of Polyetyrene", E.L.



    Ziegler, 'S.P, E. Journal, April 1954. The assemblies correspond to the equation y2 = 6x).



   EXAMPLES 19
 EMI44.6
 apation of coovmers by the exchange pro e Ld of ester groups Two moles of the bisphenol of 4-vinyl-
 EMI44.7
 oyolohexene, one mole of 2,2- (4-hydroxyph "ny1) propane, ¯ and 3.15 moles of diphenyl carbonate in a reactor, heated in an oil bath, and equipped with a stirrer, an inlet of inert gas, from a condenser-receiver system connected to a vacuum device 1. An inert gas (nitrogen) is slowly allowed to enter the system at the same time as the internal pressure is reduced by the vacuum device. The temperature is slowly raised until a temperature of about 200 ° C. is reached in the system, and then large quantities of phenol are released.



  When continuing to heat while empty (about 4 hours)

 <Desc / Clms Page number 45>

 almost all of the phenol obtained as a by-product has evolved and the polymer produced is quite viscous. Long fibers can be stretched from the hot melt. The polymer has as structure;
 EMI45.1
        or. the two polymer units return randomly along the polymer chain.



   EXAMPLE 2
 EMI45.2
 Manufacture of co 01 eetexs ar lo x direct phoegenation process
The procedure of Example 18 is repeated with the mixture of this Example 18, except that it is replaced.
 EMI45.3
 this 0.05 mole of phosgene per 0.05 mole of iaophthaloyl dichloride. The resulting polymer contains approximately 1% ester-isophthalic linkages and 90% carbonate linkages. The physical properties are:
 EMI45.4
 Th: 175 C; 124,175 C; secant modulus at 1 5, 2.1 x 104 kg / om2; elongation at break: 60 zoo; breaking stress, 6.3 x 102 kg / cm2.



     EXAMPLE 21
 EMI45.5
 ± âLr-Mlï-o.n ¯u -djehl-oxqeorriiate Au p ng -dt y L2. pentadiene A suspension of 25.4 g (0.0795 mol) of
 EMI45.6
 dicyolopentadien biaphenol and 250 ml of toluene,

 <Desc / Clms Page number 46>

 o Contained in a three-necked round-bottomed flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and a stopper funnel, 16.5 g (0.167 mol) of phosgene are added. A solution of 19.25 g (0.195 mol) of dimethylaniline in 20 ml of toluene was then added dropwise through the stopper funnel. The reaction mixture is stirred at room temperature for about 2 hours.

   The insoluble dimethylaniline is separated from the reaction product by filtration and the filtrate is freed from its solvent by vacuum distillation. The residue is dissolved in 100 ml of methylene chloride and the solution is passed through a column of silica gel (2.9 x 26.2 cm).



  The product is eluted with 250 ml of methylene chloride, the eluates are pooled and the solvent is removed. The residue represents 23.03 g; it is identified by infrared absorption spectra comie being dicyclopentadiene bisphenol dichloroformate having an absorption band typical of a chloroformate carbonyl group at 5.65 microns. There is no absorption at 3.0 migrons, the characteristic absorption band of a phenolic hydroxyl group.



   EXAMPLE 22 Polymerization of bisphenol dicyclopentadiene dichloroformate
A solution of 4.45 g (0.01 mol) of dicyclopentadiene dichloroformate bisphenol in 50 ml of methylene chloride is added to a solution of
 EMI46.1
 + contains 0.8 g of sodium hydroxide in 75 ml of water in a three-necked round-bottomed flask fitted with a mechanical stirrer.

 <Desc / Clms Page number 47>

 that, a reflux condenser and a thermometer. The reaction mixture is stirred for 5 minutes, then 5 drops of triethylamine are added, and stirring is continued for 1 1/2 hours at room temperatures.



  The reaction mixture is then slowly poured into a Waring mixer containing 300 ml of isopropanol. He thus precipitated a polycarbonate which was washed in the mixer with 3 portions of 250 ml each of water.



  After drying under vacuum, the product represents 3.3 g (95% yield) and it has a reduced viscosity equal to 0.43 when measured at the concentration of 0.2 g in 100 ml of chloroform at 25 ° C. This dicyclopentadiene bisphenol polycarbonate, thus obtained, can be represented by the following structure:
 EMI47.1
 Films of this polycarbonate, cast from chloroform solutions, were used for analysis on an Instron apparatus which revealed a tensile strength of 385 kg per cm2, a tensile modulus of 21,000 kg per cm2, and an elongation of 1%. . The glass transition temperature (Tv) is 140 to 150 C.



     EXAMPLE 23 Copolymerization of Bisphenol from Dicyclopentadiene with Bisphenol A Dichloroformate
A mixture is stirred in the apparatus described in Example 6. 3.53 g (0.01 mole) of bisphenol-A dichloroformate in 50 ml of methylene chloride, 100 ml of water, 3 drops of triethylamine, 1 g of hydro-

 <Desc / Clms Page number 48>

   sodium xide, 0.1 g (0.001 mole) of phenol, and 3.20 g (0.01 mole) of dicyclopentadiene bisphenol. Stirring is continued for 5 minutes and then 3 additional drops of triethylamine are added. Stirring is continued for 1 hour at ambient temperatures.

   After precipitation of the coplymer with isopropanol in a Waring mixer, the copolymer is washed with 3 portions of 350 ml each of water. The yield of mixed polycarbonate is, after drying under vacuum, 5.84 g (97% yield). This product has a reduced viscosity in chloroform at 25 ° C. equal to 0.7 (0.2 g sample in 100 ml of chloroform). Analysis on an Instron apparatus of films of this polycarbonate cast from a chloroform solution showed a tensile strength of 420 kg per cm2, a tensile modulus of 17,500 kg per cm2, and an elongation. from 5 to 8%.

   The glass transition temperature is 150 0, and the impact resistance value of the pendulum is 0.33 kgm / cm3. The structure of this polycarbonate is shown below:
 EMI48.1
 
The polycarbonates of the present invention can be used in the manufacture of components of electrical corner-mutators and connectors) of housings and boxes for instrumenta, lenses, impellers for water pumps, etc. one can use film obtained

 <Desc / Clms Page number 49>

 Bare by extrusion of these polycarbonates for the manufacture of capacitors and for packaging.
 EMI49.1
 



  ::.: z, lPL3 24 Poly-vu.rethan obtained from -bisiphenol of 'I 4-di r, etli, ylene cyclohexane and pi.rra2ine
A solution of 0.86 g (0.01 mole) of piperazine, 1.0 g (0.025 mole) of sodium hydroxide, 0.019 g of phenol and 0.1 ml of triethylamine in 50 ml of water is introduced, in the reaction vessel described in Example 16. A solution of 4.21 g is added while stirring.
 EMI49.2
 (0.01 mol) of the bisphnol of 1,4-dimethylcne-oyolohexane dichloroformate in 50 ml of methylene chloride. After 5 minutes of stirring, the aqueous layer is decanted.



   The organic layer is washed twice with distilled water, and then with a 3 ml solution.
 EMI49.3
 from H10 to 17.6 in 100 ml of water while stirring for 1 hour. The reaction mixture is then aspirated with a solution of 1 ml of ammonium hydroxide - concentrated in 100 ml of water for 1 hour. At the end of this treatment, the pH of the aqueous layer is equal to
6.0 approx. The organic layer is washed with water until the aqueous layer is free from ions, and this organic layer is then poured into a Waring mixer containing 300 ml of isopropanol to precipitate the polyurethane from the bisphenol of 1. , 4-
 EMI49.4
 d3.mtny.éne cc.oh, e; ne that was formed.

   This polymer is washed three times in the Waring mixer with 250 ml portions each of distilled water. After drying under vacuum, a yield of 70% of

 <Desc / Clms Page number 50>

 this polyurethane, which has a reduced viscosity equal
 EMI50.1
 at 3.94 dena chloroform at 250U (coh-mlillon of 0.2 g in 100 ml of chloroform). Films cast from this polymer in chloroform solution
 EMI50.2
 that have a tensile strength of 630 kg per oni2, a tensile modula of 15,400 kg per cm2, an elongation of 7 to 50%, and a glass transition temperature of about 250 C.



   The structure of this polyurethane can be represented by the formula below:
 EMI50.3
 where "x" is an integer having sufficiently high values that it is a normally solid polymer.
 EMI50.4
 invention. The polishes herein can be used to provide tough, abrasion resistant topcoats on floors, threads, leather and rubber articles, etc.
 EMI50.5
 



  'nt "', i '1 <"' -: 'T'IL' "2 ;; 1'o7.Yurf.tri! ne from 1) j &. (. 9}) of '14 -di- ifi6 -, at Zlùne cyclohcâanc, 3t, from ninraz.no
The procedure and the apparatus of Example 16 are used with 4.49 g (0.01 mol) of bis (ortho-
 EMI50.6
 cresol) 1,4-dimOthylene-cyclohexane dichloroformate. The 1,4-dimethylone-cyclobiexane bis (ortho-cresol) polyurethane which forms is similar in its physical properties to that derived from the bisphenol of fl, 1 + -dimethylene-cyclohexane.

 <Desc / Clms Page number 51>

 



  EXAMPLE 26
 EMI51.1
 Polzinization of the dichloroòrialate of bisÇôrtho-ohl2.ropbenol) of 1 -d.mab .nQ.o c7.ohexane
The procedure and the apparatus of Example 16 are used with 4.9 g (0.01 mol) of bis (ortho-ohlo-
 EMI51.2
 nop2ônol) of dichlorotorminto da 1, .- d.m6iy, bnMaya.ā hoxane to the. instead of 'i a4-.imb'.y7.xc-cyc dichloroformate bisphenol, ohoxane.

   The polymer which forms is the polycarbonates of bis (ortho-chlorophenol) of 1 y4..d.m4'ahy, ze-CyaOhcXane,
The glass transition temperature (Tg), also referred to as the second order phase transition temperature, relates to the inflection temperatures found by plotting the elasticity curve (recovery after 1% elongation). of a film, the thickness of which is between 0.075 mm and 0.38 mm, depending on the temperature.



  A detailed explanation for determining elasticity and inflection point can be found in a
 EMI51.3
 article published by A. Brown in "Textile Research Journal", volume 25, 1955, at page 891.



   The following ASTH standard procedures are used:
Pendulum shock; ASTM D-256-56 Standard
 EMI51.4
 Tensile strength t Norma ASTI! 1? -8i2-6T Tensile modulus: ASTM D-882-56T standard
 EMI51.5
 Elongation at Break: Elm ASTM D-882-56T
The values of the reduced viscosity are obtained from the equation:
Reduced viscosity = ts - to / c. t c. to

 <Desc / Clms Page number 52>

 where ta is the flow time of the pure solvent; ts is the flow time of the polymer solution; it is the concentrate :! Polymer solution is expressed in grams of polymer per 100 ml of solution.
 EMI52.1
 



  . ,, .. r. , LE? 7 Polyilrethaiie de biaj2h6nol-do dic clo entadi%: ne A solution of 0.86 g (0.01
 EMI52.2
 mole) of piperazine, .0 g (0.025 mole) of sodium hydro:! ydo, 0.1 ml of triethylamine in 50 ml of water in the reactor described in Example 15. A solution is added while stirring. 4.45 g (0.01 mole) of dicyclopentadiene dichloroformate bisphenol in 50 ml of methylene chloride. At the end of minutes, we add
 EMI52.3
 . 0.15 ml (triethylamino, and stirring continued for 1 hour. The reaction mixture was then poured into a Waring mixer containing 300 ml of isopropanol to precipitate the dicyclopentadiene bisphenol poyurethane which has dissolved. form.

   The polymer is washed 3 times in the Waring mixer with 250 ml portions each of water. After drying under vacuum, an amount of 4.22 g (92% of theory) of this polyurethane is obtained, having a reduced viscosity equal to 0.45 in chloroform at 25 ° C. (sample of 0.2 g in 100 ml of chloroform).

   The co-polymer films, cast from a chloroform solution, have a tensile strength of 490 kg per cm2, a modulus of
 EMI52.4
 tensile strength of fl6, flU0 kg per cm2, an elongation of 10 96 and a glass transition temperature of about 200 C,

 <Desc / Clms Page number 53>

 
The structure of this polyurethane can be represented as indicated below:
 EMI53.1
 
The polyurethanes of the present invention can be used to provide tough and abrasion resistant topcoats on floors, threads, leather and rubber articles, etc.



   EXAMPLE 28
 EMI53.2
 PolY xç¯àfh¯ # nē¯4ēbis (optho-enesol) of dicyclopentadien3
The procedure and the apparatus of Example 16 are used with 4.73 g (0.01 mol) of bis (ortho-
 EMI53.3
 cresol) of dicyclopontadiene. The polyurethane of bis- (ortho-'oresol) dioyclopoútadione which is formed has similar physical properties to the adhesives of the product:
 EMI53.4
 bisphenol derivative of dicyclopentadibnea EXE, 1, .PLE 2 2 PolYt6rAatiop.aj.u dichloroformate of bis orthochlorohenol) of dicyc19p'entadien
The procedure and apparatus of Example 16 were used with 5.14 g (0.01 mole) of bis-
 EMI53.5
 (ortho-chlorophenol) dicyclopentadiene dichloroforiniate to. instead of dicyclopentadieno diohloroformate bisphenol.

   The polymer that forms is polycarbonate bis (dicyclopentadiene ortho-chlorophenol,
Glass transition temperatures (Tv)
 EMI53.6
 also referred to as second-order phase transition tomy: rrturas, relate to inflection temperatures that are found by plotting the

 <Desc / Clms Page number 54>

 curve of the elasticity (recovery after an elongation of 1%) of a film, the thickness of which is between 0.075 mm and 0.38 mm, as a function of temperature.

   A detailed explanation for the determination of elasticity and inflection point can be found in an article by A. Broum in "Textile Research Journal", volume 25, 1955, at page 891.



   The following ASTM standard procedures are used:
Pendulum shock; ASTI standard: D-256-56
Tensile strength ! ASTM D-882-56T standard - Traction module: ASTI D-882-56T standard
Elongation at Break: ASTM D 882-56T
Although the invention has been described by its preferred forms, it will be understood that the present disclosure has been made only by way of example, and that one can. bring / loads of details without going out. of the spirit and scope of the invention.
 EMI54.1



    

Claims (1)

ABSTRACT A - Manufacturing process, bisphenols, characterized by the following points, singly or in combinations: 1. A cyclic organic compound having unconjugated double bonds and at least a stoichiometric amount of a phenol having a replaceable hydrogen atom is contacted with a substantially anhydrous catalyst which is an acid exchange resin. cation agent, operating at a temperature of 30 C. to 150 C. 2. The reaction temperature is between 50 and 125 C., and in particular it is between 70 and 100 C. 3. The phenol is present in an exo-dental amount of between 3 and 20 moles, in particular between 6 and 12 moles, and in particular equal to 10 moles, of phenol per mole of cyclic reagent. 4. The catalyst is present in an amount of 0.55 to 25 parts, and especially 1 to 2 parts by weight, per 100 parts by weight of the reaction mixture. 5. Phenol is o-chlorophenol, o-oresol, alpha-naphthol or phenol. 6. The cyclic organic reagent is 1,4-dimethylene-cyclohexane, 4-vinyl-cyclohexane, dicylopentadiene or alpha-pinene. B - As new industrial products Bisphenols of cyclic organic compounds having unconjugated double bonds, these bisphenols being characterized by the following points <Desc / Clms Page number 56> singly or in combinations; 1. It is a bisphenol in which the phenolic portions are attached to different carbon atoms, this bisphenol responding to the formula: EMI56.1 where E is the saturated residue of a cyclic organic compound having unconjugated double bonds; each R is independently of the other a hydrogen or halogen atom or a hydrocarbon group free from aliphthic unsaturation or a saturated oxyhydrocarbon group, and "n" is an integer of 1 to 3. 2. It is a 1,4-dimethylene-cyclohexane bisphenol of the formula: EMI56.2 where each R and "n" have the meaning described above. 3. It is crystalline 1,4-dimethylene-cyclohexane bisphenol of the formula: EMI56.3 <Desc / Clms Page number 57> 4. Crystalline bisphenol, 1,4-dimethylene-cyclohexane has a melting point of 195 C. 5. It is 4-vinyl-cyclohexene bisphenol of the formula EMI57.1 where each R and "n" have the meaning defined above. EMI57.2 6. It is 1,3-bis- (p-hydnoxyphenyl) -1-ethyl-cyclohexane. 7. It is bisphenol ae dicyclopentadiene of the formula: EMI57.3 8. This is crystalline dicyclopentadiene bisphenol of the formula EMI57.4 9. The melting point of compound (B, 8) is between 198 and 200 C. 10. It is alpha-pinene bisphenol of formula s <Desc / Clms Page number 58> EMI58.1 where R and "n" have the meaning defined above, and A and G, which are different from each other, are a hydrogen atom or a phenyl group, 11 Alpha-pinene bisphenol, defined under (B, 10) is characterized by the following composition: EMI58.2 - Beta form Alpha form (around 65%) (around 35%) 12. These bisphenols were obtained by a process as defined under (A). C - A polcarbonate resin characterized by the following points, singly or in combinations 1. The polymer has as structure: EMI58.3 <Desc / Clms Page number 59> where E is the saturated residue of a cyclic organic compound having unconjugated double bonds; each R and "n" have the meaning defined above and "x" is a number large enough to be a normally solid polymer. 2. The polymer has as structure EMI59.1 where E, R and "n" have the meaning defined above; D is a divalent alkylidene, cycloalkylidene, ary- EMI59.2 lènet P 0 -0. .0-., -S-, -8 or s 0 ¯ 10 and "X" and "y" are numbers large enough that they are normally solid polymers. 3. The D radical is a propylidene radical. 4. R is a hydrogen atom. EMI59.3 5. E is a divalent radical 1,4-dimetbylene-cyclorhexane, 4-vinyl-cyclohaxane, dicyc7.opentadiene or alpha-pinene. D - A polyurethane resin, characterized by the following points, singly or in combinations: 1. The polymer has as structure: EMI59.4 <Desc / Clms Page number 60> where E, R, "n" and "x" have the meaning defined above. 2. R is a hydrogen atom. 3. E is a divalent 1,4-dimethylene-cyclohexene, 4-vinyl-cyclonexene, dicyclopentadiene or alpha-pinene radical,