阅读说明：本技术 酚醛清漆树脂及在橡胶组合物中的应用 (Novolac resin and the application in rubber composition ) 是由 板桥太门 大卫·P·麦克诺顿 田岛宏一郎 C·迈克尔·沃尔克普 于 2018-02-28 设计创作，主要内容包括：一种间苯二酚酚醛清漆树脂组合物,包含(i)醛或酮与(ii)芳烷基取代的间苯二酚和间苯二酚的反应产物,其中芳烷基取代的间苯二酚的摩尔数与间苯二酚和芳烷基取代的间苯二酚的总摩尔数之比为0.01:1至0.4:1。(A kind of resorcinol novolak resin compositions, reaction product comprising resorcinol and resorcinol that (i) aldehydes or ketones and (ii) aralkyl replace, the ratio between the total mole number of resorcinol that the molal quantity and resorcinol and aralkyl of the resorcinol that wherein aralkyl replaces replace is 0.01:1 to 0.4:1.)

1. a kind of resorcinol novolak resin compositions, include:

(i) include the unit limited by formula (I) resin

Wherein, R¹It is hydrogen atom or aralkyl, R²And R³At least one of be alkylidene bridge, and R²And R³In the other is Alkylidene bridge or hydrogen atom；And

(ii) the unreacted resorcinol compound limited by formula (II)

Wherein, R¹It is hydrogen atom or aralkyl, and wherein, the molal quantity of the unit often limited by formula (I) in the composition adds On the molal quantity of compound that is limited by formula (II) include to be greater than 1 mole and the aralkyl less than 40 moles.

2. composition according to claim 1, wherein the aralkyl is styryl.

3. composition according to any one of the preceding claims, wherein the list often limited by formula (I) in the composition The molal quantity that the molal quantity of member adds the compound limited by formula (II) includes the aralkyl less than 14 moles.

4. composition according to any one of the preceding claims, wherein the list often limited by formula (I) in the composition The molal quantity that the molal quantity of member adds the compound limited by formula (II) includes the aralkyl less than 10 moles.

5. composition according to any one of the preceding claims, wherein the alkylidene bridge is methylene bridge.

6. composition according to any one of the preceding claims, wherein the resin is the form of pastille or bead.

7. a kind of resorcinol novolak resin compositions, include:

(i) reaction product for the resorcinol and resorcinol that aldehydes or ketones and (ii) aralkyl replace, wherein the aralkyl takes The molal quantity of the resorcinol in generation and the ratio between the total mole number of resorcinol of the resorcinol and aralkyl substitution are 0.01:1 to 0.4:1.

8. resorcinol novolak resin compositions according to claim 7, wherein the isophthalic that the aralkyl replaces The ratio between total mole number of resorcinol that the molal quantity of diphenol and the resorcinol and the aralkyl replace for 0.01:1 extremely 0.1:1。

9. according to resorcinol novolak resin compositions described in claim 7-8, wherein between the aralkyl replaces The ratio between the total mole number of resorcinol that the molal quantity of benzenediol and the resorcinol and the aralkyl replace is 0.01:1 To 0.09:1.

10. according to resorcinol novolak resin compositions described in claim 7-9, wherein the aldehydes or ketones be selected from by Group consisting of: formaldehyde, methanol formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, crotonaldehyde, cinnamic acid, benzaldehyde, furfural, acetone and first Base ethyl ketone.

11. according to resorcinol novolak resin compositions described in claim 7-10, wherein the aldehydes or ketones are aldehyde, And the aldehyde is formaldehyde or methanol formaldehyde.

12. according to resorcinol novolak resin compositions described in claim 7-11, wherein what the aralkyl replaced Resorcinol is styryl resorcinol or methyl styrene base resorcinol.

13. according to resorcinol novolak resin compositions described in claim 7-12, wherein (i) described aldehydes or ketones with (ii) molar ratio of the aralkyl replaces resorcinol and resorcinol is about 0.5:1 to 1:1.

14. a kind of method for the resorcinol novolac resin for being used to form aralkyl substitution, which comprises

The resorcinol and resorcin reaction for replacing (i) aldehydes or ketones and (ii) aralkyl, wherein what the aralkyl replaced The ratio between the total mole number of resorcinol that the molal quantity of resorcinol and the resorcinol and the aralkyl replace is 0.01: 1 to 0.4:1.

15. according to the method for claim 14, wherein the molal quantity for the resorcinol that the aralkyl replaces and it is described between The ratio between the total mole number of resorcinol that benzenediol and the aralkyl replace is 0.01:1 to 0.1:1.

16. method described in 4-15 according to claim 1, wherein the molal quantity for the resorcinol that the aralkyl replaces and institute The ratio between total mole number of resorcinol that resorcinol and the aralkyl replace is stated as 0.01:1 to 0.09:1.

17. method described in 4-16 according to claim 1, wherein the aldehydes or ketones are selected from the group being made up of: formaldehyde, first Alcohol formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, crotonaldehyde, cinnamic acid, benzaldehyde, furfural, acetone and methyl ethyl ketone.

18. method described in 4-17 according to claim 1, wherein the aldehydes or ketones are aldehyde, and the aldehyde is formaldehyde or methanol Formaldehyde.

19. method described in 4-18 according to claim 1, wherein the resorcinol that the aralkyl replaces is between styryl Benzenediol or methyl styrene base resorcinol.

20. method described in 4-19 according to claim 1, wherein between (i) described aldehydes or ketones and (ii) described aralkyl substitution The molar ratio of benzenediol and resorcinol is about 0.5:1 to 1:1.

21. a kind of improved rubber composition, natural rubber, synthetic rubber or their combination are selected from comprising every 100 parts of (1) Diene rubber component, and the resorcinol novolac resin that (2) 0.1 to 10 parts of aralkyl replaces, the aralkyl takes Use of the resorcinol novolac resin in generation with 1mol% to about 40mol% is selected from by styrene, α-methylstyrene, β- The resorcinol of one or more compound aralkyl of the group of methyl styrene and p-methylstyrene composition.

22. rubber composition according to claim 21, wherein the resorcinol novolaks tree that the aralkyl replaces Use of the rouge with 1mol% to about 10mol% is selected from by styrene, α-methylstyrene, Beta-methyl styrene and to methylbenzene second The resorcinol of one or more compound aralkyl of the group of alkene composition.

23. according to rubber composition described in claim 21-22, wherein resorcinol styrene aralkyl.

24. according to rubber composition described in claim 21-23, wherein based on 100 parts of diene rubber component, the rubber Glue composition also includes 0.1 to 10 part of methylene donor.

25. according to composition described in claim 21-24, wherein the synthetic rubber is selected from the group being made up of: benzene second Alkene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, neoprene, isobutene-isoamyl Diene rubber, ethylene propylene copolymer and ethylene propylene diene rubber.

26. according to composition described in claim 21-25, wherein the diene rubber is natural rubber.

27. also including methylene donor according to composition described in claim 21-26, the methylene donor is selected from by six The group of methenamine, melamine methylol, etherfied methylol melamine and esterification melamine methylol composition.

Technical field

The present invention relates to resorcinol resin composition (the resorcinolic resin that aralkyl replaces Composition the rubber composition of the resorcinol resin composition preparation) and using aralkyl replaced.

Background technique

Resorcinol resin, especially novolac resin, including in the presence of excessive resorcinol resorcinol and The reaction product of aldehydes or ketones.Many useful resorcinol resins are formed by resorcinol and aldehyde, therefore are typically referenced to isophthalic two Phenol-formaldehyde resin or resorcinol-aldehyde novolac resin.

Resorcinol resin can be used for manufacturing rubber product.In general, resorcinol resin is used as the bonding in rubber formulation Agent and curing agent.As adhesive, resorcinol resin advantageously facilitate various organic in rubber and rubber composite material and The adherency of inorganic constituents.For example, many rubber composite materials are steel enhancing or fabric reinforced composite, and resorcinol tree Rouge is widely used in the adherency promoted between rubber and steel or textile cord.

Resorcinol resin is usually produced with excessive resorcinol；I.e. resin usually contain 10 to 20% it is unreacted Or free resorcinol.When balancing critical nature, the amount for the resorcinol that dissociates may be a key factor.For example, such as Fruit reduces the amount of free resorcinol, this can realize that then the softening point of resin is improved by increasing the relative quantity of aldehyde, because This is difficult with generation when rubber compounding under conventional compounding temperature.

However, the presence of free resorcinol may be problematic.For example, free resorcinol is in rubber mix process In can volatilize, this volatilization is commonly known as smoke, therefore additional problem is brought to rubber mix process.In addition, free The presence of resorcinol facilitates the hygroscopicity of resorcinol resin, this leads to the problem of storage and processing in turn.

It has made efforts to reduce these trees by modified to resorcinol in the manufacturing process of resin or addition substituent group Sow discord the amount of benzenediol in rouge middle reaches.This modification reduces the amount that can be used for the free resorcinol of smoke, but also by isophthalic two The quantity of reactive site on phenol molecule is reduced to two or less from three positions (2,4 and 6).Modified resorcinol resin Also it is less likely to absorb moisture.Therefore, it by modified resorcinol resin, has produced with low smoke and agent of low hygroscopicity Resin.These modified resins are commonly referred to as styrol resorcinol resin, usually produce by using modified resin, Modified resin is formed by styrene and resorcinol with the molar ratio reaction of about 0.4:1.For example, U.S. Patent number 5,049, 641 teach using modified resorcinol synthesis resorcinol resin, and the modified resorcinol passes through styrene and isophthalic two Phenol is formed at least molar ratio reaction of 0.25:1.Related to this, U.S. Patent number 5,021,522 is taught with aralkyl phenol Urea formaldehyde preparation it is improved can vulcanized rubber composition, aralkyl phenolic resin be used as methylene acceptor.These methylene Receptor includes each phenolic group at least aralkyl of 10mol%.

Although the advantageously low smoke of these styrol resins and low water absorbable, they are special compared with normal resin Sign is brittleness, the reactivity of reduction, and leads to higher lag in rubber compound.By resin particle it is broken show it is crisp Property be problematic because broken resin particle generates fine grained, also referred to as fine powder, generated in rubber compounding site of administration Dustiness and increase storage during resin be compacted a possibility that.The reduced reactivity of resin (is indicated, example by longer curing time As t ' 90) leads to significantly reduced yield and lower production capacity during rubber compounding site of administration use.By rubbery The high hysteresis quality for closing the increased tan δ expression of object is the instruction of the heat during using finished rubber product, and in many rubbers It is unfavorable in glue product.

Therefore, between normal resin (that is, with those of unmodified resorcinol production resin) and styrol resin Tradeoff be well-known, and technical staff is typically based on many factors and selects therebetween.For example, standard tree Rouge is commercially still critically important, and technical staff solved the problems, such as using other means it is related with smoke and hygroscopicity. In another example, in the manufacturing location that there are problems that insufficient environmental Kuznets Curves or high humility, styrol resin it is low Reactivity is acceptable.However, it is still desirable to continue to improve resorcinol resin.

Summary of the invention

Aspect of the invention provides a kind of resorcinol novolak resin compositions (resorcinolic novolac Resin composition), it includes the resins that (i) contains the unit limited by formula (I)

Wherein R1 is hydrogen atom or aralkyl, and at least one of R2 and R3 are alkylidene bridges, and another in R2 and R3 A is alkylidene bridge or hydrogen atom；The unreacted resorcinol compound that (ii) is limited by formula (II)

Wherein R1 is hydrogen atom or aralkyl, and wherein composition includes the molal quantity of the unit often limited by formula (I) In addition the molal quantity of the compound limited by formula (II) is the aralkyl greater than 1 mole and less than 40 moles.

Other aspects of the present invention provide a kind of resorcinol novolak resin compositions, and it includes (i) aldehydes or ketones The reaction product of the resorcinol and resorcinol that replace with (ii) aralkyl, mole for the resorcinol that wherein aralkyl replaces Several the ratio between total mole numbers of resorcinol replaced with resorcinol and aralkyl are 0.01:1 to 0.4:1.

Other aspects of the present invention provide a kind of resorcinol novolac resin group for being used to form aralkyl substitution The method for closing object, this method include the resorcinol and resorcin reaction for replacing (i) aldehydes or ketones and (ii) aralkyl, wherein The molal quantity for the resorcinol that aralkyl replaces and the ratio between the total mole number of resorcinol of resorcinol and aralkyl substitution are 0.01:1 to 0.4:1.

Specific embodiment

Aspect of the invention is based at least partially on the hair of the resorcinol novolak resin compositions of aralkyl substitution Existing, wherein total resorcinol aromatic ring of 1mol% to 40mol% is by one or more selected from by styrene, Alpha-Methyl benzene second The compound aralkyl of the group of alkene, Beta-methyl styrene and p-methylstyrene composition.It was unexpectedly found that relatively low Aralkylization it is horizontal under, compared with normal resin (that is, without those of aralkyl resin) and common styrene resin, The resin is advantageously characterized in that lower brittleness.Therefore, although aralkyl of the teaching in prior art with the level of signifiance The resin of change to reduce free resorcinol, but it has now been surprisingly discovered that, low-level aralkyl is provided higher Aralkylization it is horizontal under unobservable benefit.Therefore, aspect of the invention, which is related to modified resin and preparation, has low-level The method of these resins of aralkyl.Further it has been observed that these modified resins provide rubber composition, including solidification Rubber composition, show better than the rubber composition including standard resorcinol resin and common styrene resin Advantage.Therefore, other embodiments are related to the rubber composition prepared using modified resin as defined herein and vulcanized rubber.

The resorcinol novolak resin compositions that aralkyl of the invention replaces are alternatively referred to as between aralkyl substitution Benzenediol resin combination, aralkyl resorcinol resin composition or styrol resorcinol resin composition.These Composition includes the resin of (i) containing resorcinol unit and (ii) unreacted (that is, unbonded) resorcinol compound (that is, resorcinol monomer).Resorcinol unit in resin includes the resorcinol that resorcinol unit and aralkyl replace Unit (or aralkyl resorcinol unit).Technical staff recognizes the unit in resin, especially resorcinol unit, spreads out It is born from the resorcinol that resorcinol or aralkyl replace, is for example reacted by condensation reaction with aldehydes or ketones.Unreacted Resorcinol compound include resorcinol that resorcinol and aralkyl replace.

In one or more embodiments, the resorcinol resin that aralkyl replaces includes one or more by formula (I) The resorcinol unit of restriction

Wherein R¹It is hydrogen atom or aralkyl, R²And R³At least one of be alkylidene bridge, and R²And R³In another It is alkylidene bridge or hydrogen atom.Structure used in formula (I) is intended to indicate that one or more methylene bridges can be bonded to aromatic ring On 2,4 or 6 the fact.In addition, substituent R¹, especially in R¹In the case where being aralkyl, 2,4 or 6 can be located at. The skilled person will understand that in aromatic ring not with hydroxyl, R¹、R²Or R³Any carbon atom of bonding will include hydrogen atom.At one or more In a embodiment, resorcinol compound can be limited by formula (II)

Wherein R¹It is hydrogen atom or aralkyl.

In one or more embodiments, aralkyl is the residual of aralkyl dialkenyl compound and resorcin reaction Base.In specific embodiment, aralkyl dialkenyl compound includes styrene, α-methylstyrene, Beta-methyl styrene And p-methylstyrene.As the skilled person will understand that, in styrene and in the case where resorcin reaction, limited by formula (III) Fixed resorcinol compound there may be:

Wherein aralkyl substituents are (that is,-C (CH₃)(H)(C₆H₅)) it is properly termed as styryl substituent group or styryl. Technical staff recognizes styryl substituent group or group is and the styrene residue after resorcin reaction.Therefore, formula (III) Resorcinol compound can be described as 4- styryl resorcinol or more commonly referred to as styryl resorcinol.With similar Mode, alternatively, the case where aralkyl substituents are derived from α-methylstyrene, Beta-methyl styrene or p-methylstyrene Under, substituent group is alternatively referred to as methyl styrene base substituent group or group, and the compound is referred to alternatively as methylbenzene second Alkenyl resorcinol.Technical staff recognizes that styryl substituent group (or methyl styrene base substituent group) can also be with isophthalic two Other positions bonding on phenol ring, such as 2 or 6.

According to aspects of the present invention, the resorcinol resin composition that aralkyl of the invention replaces includes per (i) isophthalic The molal quantity of two phenol units (for example, being limited by formula (I)) is plus (ii) resorcinol compound (for example, being limited by formula (II) Compound) molal quantity be less than 40 moles, in other embodiments less than 14 moles, be less than in other embodiments 13 moles, in other embodiments less than 10 moles, in other embodiments less than 9.5 moles, and in other implementations Aralkyl in mode less than 9.0 moles.In these or other embodiments, the resorcinol of aralkyl substitution of the invention Resin combination includes the molal quantity of per (i) resorcinol unit (for example, being limited by formula (I)) plus (ii) resorcinol The molal quantity for closing object (for example, the compound limited by formula (II)) rubs greater than 1 mole, to be greater than 1.5 in other embodiments You, is greater than 2.0 moles in other embodiments, is greater than 2.5 moles in other embodiments, in other embodiments greatly In 3.5 moles, and the aralkyl greater than 4.0 moles in other embodiments.In one or more embodiments, this hair The resorcinol resin composition that bright aralkyl replaces includes (for example, being limited by formula (I)) per (i) resorcinol unit Molal quantity adds the molal quantity of (ii) resorcinol compound (for example, the compound limited by formula (II)) as about 1 mole to about 40 moles, about 1 mole to about 14 moles in other embodiments, about 1 mole to about 13 moles in other embodiments, In About 1 mole to about 10 moles in other embodiments, about 1 mole to about 9.0 moles in other embodiments, and at other About 1 mole to about 9.5 moles of aralkyl in embodiment.

For resorcinol compound of the invention by making resorcinol with one or more selected from by styrene, α-first The compound (that is, aralkyl dialkenyl compound) of the group of base styrene, Beta-methyl styrene and p-methylstyrene composition is anti- It should prepare.

In one or more embodiments, resorcinol compound is by making the aralkyl dialkylene of appropriate molar ratio Close object prepared with resorcin reaction, with provide comprising relative to resorcinol compound total mole number for less than 40mol% is less than 14mol% in other embodiments, is less than 13mol% in other embodiments, in other embodiment party It is less than 10mol% in formula, is less than 9.5mol% in other embodiments, and is less than 9.0mol% in other embodiments Aralkyl resulting composition.In these or other embodiments, resorcinol compound is by making appropriate molar ratio Prepared by aralkyl dialkenyl compound and resorcin reaction, to provide comprising the total mole number relative to resorcinol compound To be greater than 1.5mol% in other embodiments greater than 1mol%, it is greater than 2.0mol% in other embodiments, at other It is greater than 2.5mol% in embodiment, is greater than 3.0mol% in other embodiments, and be greater than in other embodiments The resulting composition of the aralkyl of 3.5mol%.In these or other embodiments, resulting composition includes relative to isophthalic The total mole number of diphenol compound is 1mol% to 40mol%, in other embodiments 1mol% to 14mol%, at other 1mol% to 13mol% in embodiment, in other embodiments 1mol% to 10mol%, in other embodiments 1mol% to 9.5mol%, and be in other embodiments the aralkyl of 1mol% to 9.0mol%.

The skilled person will understand that some resorcinol aromatic rings in specific novolak resin compositions can contain multiple virtues Alkyl, and other resorcinol aromatic rings can not include any aralkyl.However, the fact will not change the virtue indicated with mol% Alkyl quantifies, because molar percentage is construed to quantity of the quantity of aralkyl relative to resorcinol ring.At one or more In a embodiment, required aralkyl degree can be by being blended the resorcinol composition for example, height aralkyl It is realized with the resorcinol composition of a small amount of (including zero) aralkyl.

By making resorcinol and the desired amount of one or more selected from by styrene, α-methylstyrene, Beta-methyl benzene The compound of the group of ethylene and p-methylstyrene composition reacts to carry out aralkyl glycosylation reaction.The reaction can solvent exist or In the absence of carry out.Sometimes solvent may be beneficial.The example of suitable solvent includes benzene,toluene,xylene, ethylbenzene, alkyl Pure and mild acetone.

In order to commercially viable, it may be necessary to be catalyzed one or more selected from by styrene, α-methylstyrene, β-first The compound of group and the reacting for resorcinol of base styrene and p-methylstyrene composition.The example of suitable catalyst is not Reed Kerafyrm thatch (Friedel Crafts) catalyst and acid catalyst.The example of acid catalyst includes inorganic acid, such as salt Acid, sulfuric acid, phosphoric acid and phosphorous acid.The example of organic acid catalyst includes alkyl and aryl sulfonic acid, such as benzene sulfonic acid, two sulphur of benzene Acid, toluenesulfonic acid, xylene monosulfonic acid and methanesulfonic acid.Useful catalyst is aryl sulfonic acid catalyst.The amount of catalyst can be every Catalyst of 100 parts of the resorcinol within the scope of 0.01 to 10 part.Aralkyl glycosylation reaction is usually in 50 DEG C to 180 DEG C of temperature Lower progress.

In one or more embodiments, resin combination of the invention is usually by making resorcinol compound and aldehyde Or prepared by reactive ketone.The molar ratio of aldehydes or ketones and resorcinol can change in about 0.50:1 to 1:1, in other embodiments Be about 0.52:1 to about 0.68:1, be in other embodiments about 0.54:1 to about 0.66:1, in other embodiments for About 0.56:1 to 0.64:1, and be in other embodiments about 0.57:1 to about 0.62:1.

In one or more embodiments, aldehydes or ketones be can be selected from by formaldehyde, methanol formaldehyde (methyl formcel, first Base formaldehyde), acetaldehyde, propionic aldehyde, butyraldehyde, crotonaldehyde, cinnamic acid, benzaldehyde, furfural, acetone and methyl ethyl ketone composition group.In In specific embodiment, aldehydes or ketones are formaldehyde or methanol formaldehyde.

As discussed above, it is desired to resin can be by reacting resorcinol with aralkyl dialkenyl compound, so After make resorcinol compound with ketone or aldehyde reaction to prepare.Resorcinol aralkylization can also be made into itself and aldehyde simultaneously simultaneously Or reactive ketone.In specific embodiment, resorcinol is aralkyl first, then the resorcinol group of aralkyl Close object comprising the resorcinol and the resorcinol (isophthalic that do not react with aralkyl dialkenyl compound that aralkyl replaces Diphenol), it is reacted with aldehydes or ketones.In an alternative embodiment, (that is, in isophthalic two after preparing resorcinol novolac resin After phenol or aldehydes or ketones reaction), resin can be by aralkyl.

It those of reacts in embodiment, is supplied to wait react with aldehydes or ketones in wherein aralkyl resorcinol composition Aralkyl resorcinol composition feature can be the aralkyl in composition replace resorcinol molal quantity and The ratio between the total mole number of resorcinol that benzenediol and aralkyl replace.In one or more embodiments, in composition The ratio between the total mole number of resorcinol that the molal quantity and resorcinol and aralkyl of the resorcinol that aralkyl replaces replace can It is in other embodiments 0.01:1 to 0.14:1, in other embodiments extremely for 0.01:1 for 0.01:1 to 0.4:1 0.13:1 is in other embodiments 0.01:1 to 0.10:1, is in other embodiments 0.01:1 to 0.09:1, and It is 0.01:1 to 0.095:1 in other embodiments.

In one or more embodiments, the resorcinol novolak resin compositions of aralkyl substitution of the invention It may include being greater than 10wt%, be greater than 11wt% in other embodiments, and in other embodiments greater than 12wt%'s Free resorcinol (that is, resorcinol that is unbonded or not reacted with aldehydes or ketones).In these or other embodiments, this The resorcinol novolak resin compositions that the aralkyl of invention replaces may include being less than 25wt%, in other embodiments Less than 23wt%, and it is less than the free resorcinol of 20wt% in other embodiments.In one or more embodiments In, it is about that the resorcinol novolac resin that aralkyl replaces can include about 10 to about 25wt% in other embodiments 11 to about 23wt%, and be in other embodiments about 12 to about 20wt% free resorcinol.As technical staff will Understand, free resorcinol can be measured by liquid chromatography.

In one or more embodiments, the resorcinol novolak resin compositions of aralkyl substitution of the invention It can be characterized in that softening point is about 90 to about 120 DEG C, and in other embodiments be about 95 to about 115 DEG C.Resin it is soft Change point can with reference to the ASTM E 28 and ASTM D 6090 of latest edition being incorporated herein by reference entire contents according to Lower method measurement.Plum Teller softening point apparatus can be used in this method, may include control unit model FP-90 or equivalent Object, type of furnace FP-83 or equivalent and cartridge module, timer, porcelain evaporating dishes (diameter is about 3 ") and hot plate.This method can Use the screw pitch type cup and 440 stainless steel balls (diameter 0.2500 " and have to pass through cup) for being drilled into 0.257 " opening (F brill). The equipment can be calibrated according to ASTM D 6090.Resin sample (about 15 grams) can be in the porcelain on 600-650 °F of hotplate surface Or melted in aluminum evaporation ware, the time is about 4 minutes.After fusing, sample can be poured into the temperature for having been preheated at least molten resin In the cup of degree.The amount for the resin sample being poured into cup should make after solidification, can be removed with the scraper or putty knife of heating Extra sample.Then sample can be cooled to room temperature in drier, it then can be with assembling box, so that ball rests on resin Top.Then the box of assembling is put into furnace, furnace can be preset as lower than expected 85 DEG C or 10-15 DEG C of softening point.The rate of heat addition It can be set as 1 DEG C/min.It then can be with rotation box until its lock into place.After 30 seconds, the behaviour of softening point device can star Make, to generate the softening point measurement of completion.

The condensation reaction of aralkyl resorcinol composition (for example, composition containing resorcinol) and aldehydes or ketones can be There is no catalyst or there are carry out under catalyst.Useful catalyst includes conventional acid-catalyzed dose.Suitable acid catalyst Example it is as described above.In one or more embodiments, reaction can carry out within the temperature range of 50 DEG C to 200 DEG C. The use of solvent is optional, and suitable solvent with it is mentioned-above identical.

In one or more embodiments, the resorcinol novolac resin that aralkyl of the invention replaces be can be The form of powder, thin slice, pastille or bead.In specific embodiment, the resorcinol novolaks tree of aralkyl substitution Rouge is the form of pastille or bead.

About rubber composition of the invention, rubber composition may include rubber components, may include any natural rubber, Synthetic rubber or combinations thereof.The example of synthetic rubber includes but is not limited to styrene-butadiene-copolymer, polyisoprene, poly- fourth Diene, acronitrile-butadiene-styrene, polychlorobutadiene, polyisobutene, ethylene-propylene copolymer and Ethylene-Propylene-Diene rubber Glue.

Rubber composition may also include one or more conventional additives for this composition.The reality of these additives Example includes carbon black, cobalt salt, stearic acid, silica, silicic acid, sulphur, peroxide, zinc oxide, filler, antioxidant and softening Oil.

In one or more embodiments, the resorcinol novolak resin compositions of aralkyl substitution of the invention Commonly used in rubber is adhered on reinforcing material.Optionally, reinforcing material can be reacted in advance with adhesive etc. or be coated with it. No matter whether reinforcing material coats adhesive material or pre-reaction therewith, the present invention in advance all has applicability.Suitable enhancing The example of material includes nylon, artificial silk, polyester, polyamide, glass fibre, steel, brass coated steel and galvanized steel.

Rubber composition also may include one or more methylene donor components.Methylene donor component is during vulcanization Formaldehydogenic any compound is produced when heated.The example of these compounds illustrates that this is specially in U.S. Patent number 3,751,331 Benefit is incorporated herein by reference.Preferred methylene donor compound is hexa, dihydroxymethyl melamine, three hydroxyls Methyl melamine, tetra methylol melamine, pentamethylol melamine, hexamethylolmelamine and its mixture.Hydroxyl Methyl melamine, which can be, to be completely or partially etherified or esterification, such as hexa methoxy melamine methylol.Methylene supplies The concentration that body can be about 0.1 to 15 part with every 100 parts of rubber exists, or in other embodiments, is with every 100 parts of rubber 0.1 to 10 part of concentration exists.The ratio for the resorcinol novolac resin that methylene donor and aralkyl replace can be 1: 10 to 10:1.

As should be understood, rubber components, additive, reinforcing material and methylene donor compound are known.In addition, The method of vulcanising composition is known.Improvement of the invention is related to the resorcinol novolac resin of aralkyl substitution.

The amount for the resorcinol novolak resin compositions that aralkyl in rubber compound replaces is usually every 100 weight The rubber for measuring part is 0.5 to 10 parts by weight.In other embodiments, which can be 1 to 5 part.

Rubber composition is made and used to make and use the usual manner of these compositions.

Rubber composition produced by the invention can be used for various rubber applications or rubber product.Of the invention is uncured And cured rubber composition can be used for tire applications or be used to prepare the part of tire, such as tire tread, belt spreading Other regions of mixture (belt skim stock), side wall, bead compound, automobile chassis or tire.Other application includes It can be used for the rubber product of engine support and casing.The uncured and solidification of the invention that wherein can be used or be used to prepare The other application example of rubber composition include technology or mechanical rubber good, such as hose, pneumatic band and conveyer belt.