CN108431114A - Novel alkyl phenolic resin and preparation method thereof - Google Patents
Novel alkyl phenolic resin and preparation method thereof Download PDFInfo
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- CN108431114A CN108431114A CN201680069573.7A CN201680069573A CN108431114A CN 108431114 A CN108431114 A CN 108431114A CN 201680069573 A CN201680069573 A CN 201680069573A CN 108431114 A CN108431114 A CN 108431114A
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Abstract
Here it provides using the composition of alkyl aldehydes and phenol, method and resin.In one embodiment, including the composition of alkyl phenol resin can be selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin and combination thereof by being condensed at least one phenolic monomers；And prepared by least one alkyl aldehydes with 5 12 atom alkyl groups.The alkyl phenol resin of the application is free of octyl phenol or nonyl phenol monomer.In one embodiment, formaldehyde can be used to prepare for alkyl phenol resin, alternatively, in another embodiment, alkyl phenol resin can not use formaldehyde and prepare.The method for preparing these new alternative alkyl phenol resins is method that can be cost-effective and is easy to amplify.
Description
Background technology
Related application data
This application claims the U.S. Provisional Application No.62/248 that on October 29th, 2015 submits, 114 equity wherein should
The full content of application is incorporated herein by reference.
Invention field
The present invention relates to resins and preparation method thereof.The present invention is more particularly directed to alkyl phenol resins and preparation method thereof.
Background technology
Known octyl phenol will produce environmental problem.For example, since 1976, just there is a voluntary compliance agreement in Britain, i.e.,
This kind of compound is not used in production detergent.In the world, " OSPAR pacts " suggests the use for being phased out octyl phenol,
And it is classified as the substance that take it priority action by Helsinki pact, which protects Northeast Atlantic Ocean and wave respectively
The marine environment in the sea of sieve.
Nonyl phenol also will produce environmental problem.Environmental Protection Agency USA thinks that nonyl phenol in the environment, especially exists
Persistently exist in aquatic environment, and with appropriate bioaccumulation and has great toxicity to aquatile.U.S. environment
Protection office, which is additionally considered that during nonyl phenol measures in vitro and in vivo, shows estrogenic properties.
On September 25th, 2014, Environmental Protection Agency USA propose a new great use rule, it is desirable that are opened in manufacturer
Dynamic or recovery uses progress Institutional Review before 15 nonyl phenols (NP) and nonyl phenol ethoxylate (NPE).
Octyl phenol and nonyl phenol are all usually used in producing alkyl phenol resin.The field for producing alkyl phenol resin will
Can expect, using reduction or even without octyl phenol and/or nonyl phenol monomer prepare the resin, to which production has very
Less or without octyl phenol or the resin of nonyl phenol monomer.
Summary of the invention
On the one hand, the present invention is composition, and it includes alkyl phenol resins, and the resin is by including mixture below
It is prepared by condensation reaction：Phenolic monomers are selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin,
And combination thereof；And at least one alkyl aldehydes with 5-12 atom alkyl groups.
On the other hand, the present invention is the method for preparing alkyl phenol resin, including makes to carry out comprising mixture below
Condensation reaction：Phenolic monomers, selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin and it
Combination；And at least one alkyl aldehydes with 5-12 atom alkyl groups.
At yet another aspect, the present invention is using the alkylphenol tree prepared comprising reaction mixture below by condensation
Product prepared by fat：Phenolic monomers are selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin,
And combination thereof；And at least one alkyl aldehydes with 5-12 atom alkyl groups.
Provide environmentally acceptable solution using the alkyl phenol resin of the application, to overcome with by pungent
The relevant conjunction rule problem of normal alkyl phenolic resin derived from base or nonyl phenol.In some embodiments, the alkenyl phenol tree
Fat is without octyl phenol and nonyl phenol monomer (residue or other forms).In other embodiments, the alkene of the application
Base phenolic resin also can be free of formaldehyde.
Detailed description of the invention
In a kind of embodiment of the present processes, alkyl phenol resin is the contracting by including mixture below
Close prepared by reaction：At least one alkyl aldehydes and at least one phenolic monomers, selected from phenol, cresols, resorcinol, diformazan
Phenol, ethyl -phenol, alkyl-resorcin, isomers and combination thereof.Suitable isomers includes that o-, m- and p- position is different
Structure body, such as o-, m- and p- cresols, and the isomers may be used to the present processes.
For the purpose of the application, alkyl-resorcin is the dihydroxy for the alkyl chain being present in one or two on ring
Base benzene.The alkyl chain can have 1-3 carbon.
The alkyl aldehydes that can be used for the present processes are any aldehyde with 5-12 atom alkyl groups.In some realities
It applies in scheme, alkyl aldehydes can be selected from 3,5,5- trimethyl hexanals, aldehyde C-9,2- ethyl hexanals and combination thereof.
It is important to note that, the present processes can be real in the case where being substantially absent from octyl phenol and nonyl phenol
It applies.For the purpose of the application, term " being substantially absent from " refers to the octyl phenol and nonyl phenol monomer of phenolic monomers
A concentration of 0% to less than 5%, by the total weight of phenolic monomers.In some embodiments, these monomers is a concentration of by weight
Gauge 0% is to less than 1%.In yet other embodiments, these monomers a concentration of by weight 0% to less than 0.1%.
In a kind of embodiment, phenolic monomers are free of octyl phenol and nonyl phenol.
Alkyl phenol resin can also be the form of novolaks and resol.For forming alkyl as described herein
For phenolic resin, when being prepared using base catalyst, then resol is formed, and when being prepared using acid catalyst,
Then form novolac resin.The example of suitable base catalyst includes sodium hydroxide, barium hydroxide, potassium hydroxide, hydroxide
Calcium, organic amine, sodium carbonate and combination thereof.The example of suitable acid catalyst includes hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulphur
Amic acid, halogenated acetic acids and combination thereof.For example, in one embodiment, being used to prepare the alkenyl phenol aldehyde of the present invention
The acid catalyst of resin is p-methyl benzenesulfonic acid or dodecyl benzene sulfonic acid.
In addition, preparing alkyl phenol resin, mole of the reactant used in reaction for Phenol Monomer and aldehyde reaction
Than the molecular structure and physical property that can determine resin in some embodiments.When expectation prepares phenolic varnish type resin,
Aldehyde：The ratio between phenol is 0.5：1 to 1：1 (such as 0.5：1-0.8：1) together with acid catalyst that the phenolic aldehyde for forming thermoplastic characteristics is clear
Coating resins.Higher aldehyde：The ratio between phenol is (for example, more than 1：1-3：1) resol will be formed together with base catalyst, the tree
Fat is characterized in that the ability of thermmohardening at elevated temperatures.
When being related to presence or absence of formaldehyde, the alkyl phenol resin of the application can be at least three kinds of different embodiment party
In case.
In one embodiment, alkyl phenol resin is the form of the resin without formaldehyde.For the alkane without formaldehyde
The molar ratio of base phenolic resin, aldehyde and phenolic monomers can be about 0.75：1- about 0.9：1, for example, 0.85：1.Alkane without formaldehyde
Base phenolic resin, which has, is less than 2000 dalton, for example 1000 to the molecular weight (Mw) less than 2000 dalton.
When alkyl phenol resin is the form of the resin without formaldehyde, by at least one alkyl aldehydes of progress and at least
It is prepared by the condensation reaction of phenolic monomers and reaction mixture without formaldehyde (formaldehyde monomers) a kind of.In a kind of embodiment
In, alkylphenol and alkyl aldehydes are reacted in the presence of acid catalyst.Suitable acid catalyst includes, but are not limited to inorganic acid
Or organic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulphonyl amino acid, halogenated acetic acids or combination thereof.Alternatively, alkylphenol and
Alkyl aldehydes are reacted in the presence of acid catalyst.Alkyl phenol resin can form novolac resin when using acid catalyst,
And resol can be formed when using base catalyst.
In another embodiment, formaldehyde is used to form alkyl phenol resin.Alkyl phenol resin containing formaldehyde can be phenol
Novolac resin and resol.The novolac resin can have the molecular weight of -50000 dalton of 2000 dalton,
And resol can be with the molecular weight of -20000 dalton of 2000 dalton.
For the alkyl phenol resin containing formaldehyde, molar ratio can be described below in multistep method.For having 2000
The ratio between mole of the novolac resin of the molecular weight of Er Dun -50000 dalton, aldehyde and phenolic monomers that the first step can have can
It is about 0.25：1- about 0.9：1, more preferably from about 0.5：1- about 0.85：1, and in second step formaldehyde and phenolic monomers mole
Than can be about 0.25：1- about 0.75：1, more preferably from about 0.25：1- about 0.5：1.For having -20000 dalton of 2000 dalton
Molecular weight first rank phenolic resin, the ratio between mole of aldehyde and phenolic monomers that the first step can have is about 0.25：1- is about
0.9：1, more preferably from about 0.5：1- about 0.75：1, and the ratio between mole for the formaldehyde and phenolic monomers that can have in second step can
It is about 0.25：1- about 1.25：1, more preferably from about 0.5：1- about 1：1.
For all embodiments, organic solvent can be used for condensation reaction, which can form altogether with water
Boil object.For example, in some embodiments of the present processes, n-butanol, toluene, dimethylbenzene can be used in this way, and its mix
Close object.It in one embodiment, can be by solvent and reaction-ure mixture heating to remove water in the temperature of about 200 DEG C of about 90-.
In some embodiments, temperature range can be about about 160 DEG C of 100-.
In some embodiments, solvent is also removed in condensation reaction or later.In other embodiments,
The solvent for not discharging proton under condensation condition may retain in the product after condensation reaction.
After resin is formed, catalyst can be neutralized.Resin can be used directly or be used after catalyst neutralisation.Condensation
The resin of method can be diluted, or can further be diluted with aliphatic and/or aromatic hydrocarbons or hydrocarbon mixture, the hydrocarbon or hydrocarbon mixing
Object such as petroleum distillate, kerosene, decane, pentadecane, toluene, dimethylbenzene, ethylo benzene or known to persons of ordinary skill in the art
Other available commercial solvents.
The alkyl phenol resin of the application is free or substantially free of octyl phenol or nonyl phenol monomer.These resins
Formaldehyde can be free of to prepare.The method for preparing these new alternative alkyl phenol resins is method that can be cost-effective and is easy to put
Greatly.
One of the present processes is the advantage is that alkylation and polymerisation can be carried out at the same time in a step.This can be with
Significant cost advantage is provided, especially in business amplifieroperation.
In normal alkyl phenolic resin, alkyl chain is connected to the contraposition of phenol ring as side group, and in the alkyl of the application
In phenolic resin, alkyl chain plays the bridge between two phenol rings, and it is a part for principal polymeric skeleton.Due to
Unique difference of this polymer architecture, resin are expected to have unique chemical property.
The Comparative dissolution number of degrees (RSN) value of alkylphenol urea formaldehyde is less than similar mass derived from octyl or nonyl phenol
Normal alkyl phenolic resin.RSN is the method for the hydrophobe-hydrophile composition of wherein determining nonionic surfactant.RSN values are productions
Water needed for raw persistence or permanent turbidity.Generally speaking, these the new alkyl phenol resins reported herein it is opposite
The dissolving number of degrees (RSN) value is about 7.5- about 12.5, for example, about 8- about 10.5, the phase which works as and prepared by nonyl phenol and formaldehyde
Lower, Bakelite PF6920CL when being compared like the Bakelite PF6920CL nonyl phenol novolac polymers of molecular weight
The typical RSN values range of resin is in 13.0-17.0.
Another advantage of the new method of the present invention is its multifunctionality, can be by alkyl by using a small amount of formaldehyde
Phenolic resin is converted to the novolac resin of higher molecular weight and can also convert them to heat-setting first rank phenol
Urea formaldehyde.At the same time, the use of mixed aldehyde technology reduces the release of formaldehyde.
Embodiment
It is in order to illustrate the present invention to provide following embodiment.These embodiments are not intended to limit the scope of the present invention, it
Should not so be explained.Unless otherwise indicated, all amounts are indicated with parts by weight or weight percent.Molecular weight passes through
GPC is determining and is Mw(weight average molecular weight).
Embodiment 1
Alkyl phenol resin without formaldehyde is prepared according to following methods：
1) phenol is added, 4- dodecyl benzene sulfonic acid and aromatic hydrocarbon solvent are (naphthalene depleted；Sure150ND)；
2) heating response device content is to 100 DEG C；
3) gradually feed 3,5,5- trimethyl hexanals；
4) reaction temperature is improved to 130 DEG C and 2-4 hours after flowing back；
5) it is removed water 6-10 hours at 140 DEG C by azeotropic mixture distillating method；
6) it is neutralized with 50% sodium hydroxide；
7) residual water and solvent is evaporated in vacuo, then hot melt is poured on clean plate.
The ratio between phenol and 3,5,5- trimethyl hexanals are 0.85.The molecular weight of gained alkyl phenol resin is 1,812 and more
Dispersibility is 2.24.FTIR and13Also positive confirmation polymer is formed for C-NMR spectrograms.The Comparative dissolution number of degrees (RSN) value is
10.4, less than the Bakelite PF6920CL nonyl phenol novolaks of the similar mass prepared by nonyl phenol and formaldehyde
Polymer, the typical RSN values ranging from 13.0-17.0 of Bakelite PF6920CL resins.
Embodiment 2
Alkyl phenol resin without formaldehyde is prepared according to following methods：
1) phenol is added, 4- dodecyl benzene sulfonic acid and aromatic hydrocarbon solvent are (naphthalene depleted；Sure150ND)
2) heating response device content is to 100 DEG C；
3) gradually feed 3,5,5- trimethyl hexanals；
4) reaction temperature is improved to 130 DEG C and 2 hours after flowing back；
5) it is removed water by azeotropic mixture distillating method after flowing back；
6) light vacuum is added after 5-7 hours to remove the water of existing last volume；
7) reaction flask is cooled to 40 DEG C；
8) it is neutralized with 50% sodium hydroxide；
9) it mixes 10 minutes, resin solution is then poured into container.
The ratio between phenol and 3,5,5- trimethyl hexanals are 0.73.The molecular weight of gained alkyl phenol resin is 1,292, and phase
It is 9.73 to the dissolving number of degrees.
Embodiment 3
Novolaks alkyl phenol resin is prepared according to following methods：
1) phenol is added, 4- dodecyl benzene sulfonic acid and aromatic hydrocarbon solvent are (naphthalene depleted；Sure150ND)
2) heating response device content is to 100 DEG C；
3) gradually feed 3,5,5- trimethyl hexanals；
4) pass through the 7-10 hours water for removing collection of passing at any time of azeotropic mixture distillating method reflux at 120 DEG C；
5) reaction temperature is reduced to 100 DEG C；
6) 50% formaldehyde was slowly fed in 30-60 minutes time；
7) reaction is flowed back 2 hours at 100 DEG C；
8) it is removed water 5 hours at 130 DEG C by azeotropic mixture distillating method；
9) reaction mixture is cooled to 40 DEG C；
10) it is neutralized with 50% sodium hydroxide；
11) reaction temperature is improved to 120 DEG C to be distilled under light vacuum；
12) it when seldom water is generated to no water, slightly cools down and pours out.
The ratio between phenol and 3,5,5- trimethyl hexanals are 0.5.The ratio between phenol and formaldehyde are 0.50.Gained novolac resin
Molecular weight be 18,889, and the Comparative dissolution number of degrees be 7.94.
Embodiment 4
Second of novolaks alkyl phenol resin is prepared substantially the samely with embodiment 3.Its molecular weight is 53,
734 and the Comparative dissolution number of degrees be 8.17.
Embodiment 5
The third novolaks alkyl phenol resin is prepared substantially the samely with embodiment 3.Its molecular weight is 17,
415。
Embodiment 6
First rank phenolic aldehyde alkyl phenol resin is prepared according to following methods：
1) phenol and 4- dodecyl benzene sulfonic acid is added；
2) 95 DEG C are heated to；
3) aldehyde C-9 is fed；
4) it flows back 5 hours at 130 DEG C；
5) butanol is added；
6) 60 DEG C are cooled to and is slowly added to 50% sodium hydroxide；
7) start formaldehyde charging at 65 DEG C；
8) being heated to 85 DEG C makes after the reflux of first rank phenolic aldehyde at most 5 hours；
9) 40 DEG C are cooled to, 37.5% phosphoric acid is then added to neutralize；
10) 65 DEG C are heated to be evaporated in vacuo；
11) when seldom water or butanol to no water or butanol generate, stop being evaporated in vacuo and methanol is added；
12) it is filtered by 25 micron filter bags.
The ratio between phenol and 3,5,5- trimethyl hexanals are 0.75.The ratio between phenol and formaldehyde are 1.22.Gained first rank phenolic aldehyde tree
The molecular weight of fat is 4,108.Percent solids concentration is 61.9%.It is similar to standard resol, the DSC of the resin
Show two different transition, one at 154.8 DEG C, another shows that it is heat cross-linking at 213.5 DEG C.
Embodiment 7
Second of first rank phenolic aldehyde alkyl phenol resin is prepared substantially the samely with embodiment 6, in addition to phenol and formaldehyde it
Than being 1.22.The molecular weight of the resin is 22,392 and the Comparative dissolution number of degrees are 7.49.Percent solids concentration is 59.9%.
Embodiment 8
Novolaks alkyl phenol resin is prepared according to following methods：
1) phenol and 4- dodecyl benzene sulfonic acid is added；
2) 100 DEG C are heated to；
3) gradually feed 2- ethyl hexanals；
4) 7-10 hours are flowed back to remove the water collected at any time by azeotropic mixture distillating method at 120-140 DEG C；
5) reaction mixture is cooled to 100 DEG C；
6) gradually fed formaldehyde within 30-60 minutes time；
7) it flows back 2 hours at 100 DEG C；
8) it is removed water 5 hours at 130 DEG C by azeotropic mixture distillating method；
9) reaction flask is cooled to 40 DEG C；
10) 50% sodium hydroxide is added to neutralize batch of material；
11) 120 DEG C are heated to be distilled under light vacuum；
12) it when seldom water is generated to no water, discharges vacuum and reactor content is poured into plate.
The ratio between phenol and 2- ethyl hexanals are 0.75 and the ratio between phenol and formaldehyde are 0.25.Point of gained novolac resin
Son amount is 1781, and the Comparative dissolution number of degrees are 11.8 and softening point is 98 DEG C.The softening point of the resin is by octyl phenol and formaldehyde
In the range of the standard octyl phenol novolac resin of preparation.
Although describe and illustrating the present invention, those skilled in the art by reference to specific embodiment
It will recognize that the variation that the present invention is suitable for illustrate herein.
Claims (19)
1. a kind of composition, it includes the alkyl phenol resins prepared comprising reaction mixture below by condensation：
At least one phenolic monomers, selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin and
Combination thereof；And
At least one alkyl aldehydes with 5-12 atom alkyl groups.
2. a concentration of the 0% of composition described in claim 1, the wherein octyl phenol of the phenolic monomers and nonyl phenol monomer
To being less than 5%, by the total weight of phenolic monomers.
3. composition described in claim 1, the wherein phenolic monomers are free of octyl phenol and nonyl phenol monomer.
4. composition described in claim 1, the wherein condensation reaction are free of formaldehyde.
5. composition described in claim 1, the wherein condensation reaction further include formaldehyde.
6. composition described in claim 1, the wherein alkyl phenol resin include novolac resin or resol.
7. composition described in claim 1, the wherein condensation reaction further include acid catalyst, base catalyst, You Jirong
Agent or combination thereof.
8. the method for preparing alkyl phenol resin, including condensation include reaction mixture below：
At least one phenolic monomers, selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl-resorcin, and
Combination thereof；And
At least one alkyl aldehydes with 5-12 atom alkyl groups.
9. a concentration of the 0% of method according to any one of claims 8, the wherein octyl phenol of the reaction mixture and nonyl phenol monomer
To being less than 5%, by the total weight of phenolic monomers.
10. method according to any one of claims 8, the wherein condensation reaction are free of formaldehyde.
11. method according to any one of claims 8, the wherein reaction mixture further include formaldehyde.
12. method according to any one of claims 8, the wherein alkyl phenol resin include novolac resin or resol.
13. method according to any one of claims 8, the wherein reaction mixture further include acid catalyst, base catalyst, You Jirong
Agent or combination thereof.
14. a kind of product is prepared using the alkyl phenol resin prepared comprising reaction mixture below by condensation：
At least one phenolic monomers are selected from phenol, cresols, resorcinol, xylenol, ethyl -phenol, alkyl and alkyl resorsinols
Diphenol and combination thereof；And
At least one alkyl aldehydes with 5-12 atom alkyl groups.
15. the product described in claim 14, the wherein octyl phenol of the reaction mixture and nonyl phenol monomer is a concentration of
0% to less than 5%, by the total weight of phenolic monomers.
16. the product described in claim 14, the wherein condensation reaction are free of formaldehyde.
17. the product described in claim 14, the wherein reaction mixture further include formaldehyde.
18. the product described in claim 14, the wherein alkyl phenol resin include novolac resin or resol.
19. the product described in claim 14, the wherein reaction mixture further include acid catalyst, base catalyst is organic
Solvent or combination thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201562248114P | 2015-10-29 | 2015-10-29 | |
| US62/248,114 | 2015-10-29 | ||
| PCT/US2016/059038 WO2017075166A1 (en) | 2015-10-29 | 2016-10-27 | Novel alkylphenol resins and a method of preparing thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108431114A true CN108431114A (en) | 2018-08-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201680069573.7A Pending CN108431114A (en) | 2015-10-29 | 2016-10-27 | Novel alkyl phenolic resin and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412058A (en) * | 1989-01-25 | 1995-05-02 | Ceca S.A. | Novolaks of the phenol-dense aldehyde type |
| CN1629116A (en) * | 2004-09-01 | 2005-06-22 | 中国乐凯胶片集团公司 | Process for preparing bisphenol compounds |
| CN102741306A (en) * | 2009-10-20 | 2012-10-17 | 罗地亚经营管理公司 | Modified polyamide composition containing at least one phenolic compound |
| CN104487477A (en) * | 2012-07-13 | 2015-04-01 | 迈图专业化学股份有限公司 | Polymeric materials and methods for making the polymeric materials |
-
2016
- 2016-10-27 CN CN201680069573.7A patent/CN108431114A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412058A (en) * | 1989-01-25 | 1995-05-02 | Ceca S.A. | Novolaks of the phenol-dense aldehyde type |
| CN1629116A (en) * | 2004-09-01 | 2005-06-22 | 中国乐凯胶片集团公司 | Process for preparing bisphenol compounds |
| CN102741306A (en) * | 2009-10-20 | 2012-10-17 | 罗地亚经营管理公司 | Modified polyamide composition containing at least one phenolic compound |
| CN104487477A (en) * | 2012-07-13 | 2015-04-01 | 迈图专业化学股份有限公司 | Polymeric materials and methods for making the polymeric materials |
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Application publication date: 20180821 |