CN102190603A - Non-estrogenic alkylphenol derivatives - Google Patents

Abstract

A method of making phenol and alkylphenol ethoxylates non-estrogenic by inserting 1 mole of propylene oxide onto the phenolic group before proceeding with the addition of ethylene oxide or mixtures of ethylene and propylene oxide. The final phenolic products can be further reacted to form sulfates, sulfonates, phosphate esters, condensed alkylphenol alkoxylates and other derivatives of alkylphenol or phenol. Non-estrogenic phenol and alkylphenol alkoxylates and their derivatives have been found to be excellent salt tolerant, high temperature stable surfactants for oil recovery from subterranean reservoirs. These products are also useful in forming emulsions of heavy crude for transportation through pipelines.

Description

Non-oestrogenic hormon alkylphenol derivative

The cross reference of related application

The application is based on No. the 61273005th, the provisional application of submitting on July 30th, 2009.

About the research of federal funding or the statement of exploitation

Inapplicable

The description of appended appendix

Inapplicable

Technical field

The present invention relates generally to the tensio-active agent field, more specifically, relates to the method for making non-oestrogenic hormon (non-estrogenic) alkoxylate phenol and alkylphenol and anionic derivative thereof.The invention still further relates to the application in various processes with non-oestrogenic hormon alkoxylate phenol and alkylphenol, described process includes but not limited to use oil recovery, heavy oil conveying, deinking, emulsion breaking, letex polymerization, Agrotechnical formulation, coating and tackiness agent, digging, personal care product, laundry and the Betengent product of alkylphenol ethoxylate and derivative thereof.

Background technology

In the past, alkylphenol and phenol ethoxylate have been widely used in multiple application.These application include but not limited to deinking, emulsion breaking, letex polymerization, Agrotechnical formulation, oil recovery, coating and tackiness agent, digging, personal care product, laundry and Betengent product.Alkylphenol and phenol ethoxylate are found to be one of most economical effective tensio-active agent.The use of phenol ethoxylate and alkylphenol ethoxylate (APEs) and anionic derivative thereof has been subjected to strict restriction, because they are found and have oestrogenic hormon or their degraded product and be found and have oestrogenic hormon.White etc. have discussed ethoxylated alkylphenol, particularly octyl phenol, nonyl phenol (NP) and have had the oestrogenic hormon of the nonyl phenol (NP1EO) of an ethylene oxide in the paper that is entitled as " Environmentally Persistent Alkylphenolic Compounds areEstrogenic " in 1994.Jobling and Sumpter from Brunel university report in Aquatic Toxicology1993, and the nonyl phenol (NP1EC) that has the nonyl phenol (NP2EO) of 1 or 2 mole ethylene oxides and have 1 ethylene oxide carboxylicesters is found to be the oestrogenic hormon stand-in.They find to compare with estradiol, weak 1,100 times of the oestrogenic hormon of 4-tert-butyl phenol, the oestrogenic hormon of uncle's 4-octyl phenol weak 1,200 times, weak 9,000 times of the oestrogenic hormon of nonyl phenol, the oestrogenic hormon of NP1EO weak 8,500 times, weak 9,500 times of the oestrogenic hormon of NP2EO, and weak 45,500 times of the oestrogenic hormon of NP9EO.Routledge and Sumpter are published in Journal of Biological Chemistry (the 272nd volume at them, No. 6, the 3280th page～the 3288th page (1997)) paper in examined or check the constitutional features of the induced by alkyl hydroxybenzene chemical substance relevant with estrogen activity.They find, change the size of ethoxylation side chain and make its branching can influence the degree of oestrogenic hormon.They show, add 2 mole ethylene oxides and can make 165 times of oestrogenic hormon reductions in nonyl phenol, and propylene oxide (PO) group that adds branching can make 35,000 times of oestrogenic hormon reductions.In addition, such as among the WO 9706125 report, add PO more than 2 moles, oestrogenic hormon is completely lost.Before ethoxylation, add propylene oxide, can obtain not to be degraded to the product of oestrogenic hormon precursor, can before propylene oxide, degrade, do not stay any alkylphenol residue because the phenol ring has shown to the phenol ring.WO 9706125 has described the oestrogenic hormon that use propylene oxide (PO) reduces ethoxylation phenol and alkylphenol.This patent application is confirmed, added enough PO and will reduce or eliminate oestrogenic hormon before ethoxylation.By adding enough PO, with guaranteed before ethoxylation all phenol rings all with at least 1 mole of PO complete reaction, can thoroughly eliminate oestrogenic hormon.For the phenol raw material of per molecule, this can consume PO more than 2 moles usually.But, add the character that PO more than 2 moles can change final tensio-active agent, all the more so for the tensio-active agent that contains small amounts ethene.The present invention is by guaranteeing to use the PO of minimum mole number thoroughly to eliminate the improvements over the prior art of the oestrogenic hormon of ethoxylation phenol, and can not influence final surfactant properties because of adding too much PO.

In the recent period the United States Patent (USP) of announcing discloses the application of alkylphenol in lubricating oil 7,435, No. 709, wherein, alkylphenol by as hydroxy arene such as phenol with have at least 10 carbon and make greater than the alkene of 80 moles of %C20～C30 carbon.It is non-oestrogenic hormon that this product is found, yet the use of this compound in many application is restricted, because they water-soluble limited or do not have water-soluble.The very a large amount of ethylene oxide of this product needed gives that it is water-soluble.The alkyl that the present invention allows to be attached on the alkylphenol has very short chain length, and it is water-soluble to allow adding EO seldom to give product.

Summary of the invention

Main purpose of the present invention is, non-oestrogenic hormon ethoxylation phenol or ethoxylated alkylphenol and derivative thereof is provided and do not change the final character of product by the PO that uses Texacar PC to add minimum required mole number.

Another object of the present invention is, the cost-effective non-oestrogenic hormon surfacant with widespread use is provided.

Another purpose of the present invention is, the non-oestrogenic hormon surfacant that can be used for high temperature, the application of high electrolytic solution patience is provided.

Another object of the present invention is to, be provided for emulsification and conveying crude oil and bituminous method and composition, described method and composition uses non-oestrogenic hormon ethoxylation phenol or ethoxylated alkylphenol and derivative thereof.

As described herein, use before with the EO alkoxylate Texacar PC in phenol and alkylphenol compound, to introduce PO the method for introducing these cost-effective tensio-active agents once more and overcoming the obstacle that causes because of its oestrogenic hormon is provided.

Other purpose of the present invention and advantage will be apparent by following description, wherein, will come open embodiments of the present invention in the mode of explanation and example.

Embodiment

This paper provides detailed description of the preferred embodiment.But should be understood that the present invention can implement in every way.Therefore, detail disclosed herein should not thought restriction to claim, and should be seen as the basis of claim, and be that instruction those skilled in the art use representative basis of the present invention with any in fact suitable concrete system, structure or mode.

According to preferred implementation of the present invention, a kind of method for preparing alkoxylate phenol, alkoxylated alkylphenol and the derivative thereof of non-oestrogenic hormon is disclosed, described method with phenol or alkylphenol and Texacar PC reaction, was reacted with at least 1 mole propylene oxide (PO) to guarantee every moles of phenol or alkylphenol before ethoxylation.By using 1.0 moles～1.2 moles Texacar PCs to replace 2 moles～3 moles PO can realize transforming fully.In the technical bulletin (Technical Bulletin) that is entitled as " Jeffsol AlkyleneCarbonates Alkoxylation of Phenols and Phenolic Resins " of Huntsman this is described, this technical bulletin is claimed, " be different from the reaction of using oxyethane, not using significantly, excessive alkylene carbonate promptly can obtain to react completely conversion.Usually, use as few as 2% excessive carbonic ether, can realize aromatic hydroxy, amine or thiol moiety＞99% transformation efficiency.On the contrary, guarantee to obtain similar transformation efficiency, but need 100%～300% excessive oxyethane.”

The present invention relates to the Texacar PC of 1 mole～1.2 moles of in phenol, alkylphenol or dialkyl phenol (show down structure I) addings, be converted at least 1 mole of PO adducts with all reaction site of guaranteeing phenol, alkylphenol or dialkyl phenol molecule.Then, can in molecule as described below, add EO, PO and the oxybutylene (BO) of aequum, to obtain required performance characteristics.Following structure I I has summarized composition of the present invention:

Wherein:

R and R ₁Separately separately and independently=H, C1～C24 straight chain or the alkyl of branching or the alkylidene group of C2～C24 straight chain or branching,

x＝1，

y＝1～30，

z＝0～30，

M＝H、SO ₃A、SO ₄A、COOA、PO ₄A，

A=H, Na, K, NH ₄, amine, Ca, Mg,

Q=SO ₃Or C1～C30 alkyl sulphonyl, and,

a＝0～2。

In addition, preparing non-oestrogenic hormon condensation alkyl phenolic alkoxy thing is also contained in the scope of the invention, described preparation is by method well known to those skilled in the art, molecule and formaldehyde reaction with two above structure I I, thereby form the condensation alkyl phenolic alkoxy thing of following structure III, wherein, n=2 or greater than 2, and all other symbols are same as described above.

Structure III

Effectiveness of the present invention under following examples have illustrated compared with prior art.

List of drawings

Fig. 1 has shown the relative oestrogenic hormon that various amphyls are compared with estradiol.

Fig. 2 has shown the distribution that obtains with various degree of alkoxylation.

Following examples are given their non-estrogen in order to explanation thereby utilize propylene carbonate to add 1 mole propylene oxide, compare with the product that does not add 1 mole propylene oxide, and this can not affect the performance of corresponding product.

Embodiment 1: the comparison of the estrogen of various alkyl phenolic alkoxy things

Table I has shown the relative estrogen that various alkoxylated alkylphenol are compared with estradiol with Fig. 1, and described estradiol is designated to have unit estrogen value. As can be seen from the table, compare with other product (that is, containing the ethylene oxide of various amounts and/or the nonyl phenol of propylene oxide (NP) derivative), uncle's 4-octyl phenol, 4-tert-butyl phenol and nonyl phenol have higher estrogen. Even every mole of alkyl phenol of the nonyl phenol of ethoxylation has as many as 9 mole ethylene oxides (EO), still can demonstrate some residual not oxyalkylated nonyl phenols. Utilize art-recognized standard test procedure and stimulate the result of the test of vitellogenin gene expression in the trout liver cell, all products that contain PO/ nonyl phenol molecule more than 2 moles all do not demonstrate any estrogen that detects (" Detergent Components in Sewage Effluent... " of list of references: Jobling etc., and White, " the Environmentally Persistent Alkylphenolic Compounds Are Estrogenic " of R etc., Endocrinology, the 135th volume, No. 1, the 175th page～the 182nd page). Should also be noted that, nonyl phenol with the reaction of 1 mole of propylene carbonate does not show estrogen, and with use as known in the art the base catalysis propylene oxide and utilize corresponding 1 mole of propoxylate of standard propoxylation program preparation to compare the amount with lower free nonyl phenol.

Table I has shown that the nonyl phenol such as the ethoxylation of 9 moles of adduct equal altitudes does not have estrogen, but in sewage disposal process, biodegradation is short chain ethoxylate and carboxylic acid derivates and finally becomes alkyl phenol described alkylphenol ethoxylate by the shortening of ethoxylation chain, and they all have estrogen. Table I shows, compares with not having substituent equivalent, and the estrogen of short chain ethoxylate is lower, but the similar propylene oxide derivative of size has but caused the bigger reduction of activity for the replacement of hydroxyl. (primary branched) biodegradation of ethoxylated alkylphenol of uncle's branching causes the generation of estrogen metabolin, but secondary hydroxyl can't be oxidized to carboxylate by bacterial activity, therefore, the biodegradation of propoxylation alkyl phenol can not cause the formation of estrogen intermediate.

The relative estrogen of Table I

	Relative estrogen	Free alkyl phenol %
			Estradiol	1.000000
Uncle's 4-octyl phenol	0.00037	100
			The 4-tert-butyl phenol	0.00016	100
Nonyl phenol	0.000111	100
			NP+2EO	0.000006	0.044
NP+9EO	0.0000002	0.000
			NP+1PO	0.0000013	1.17
NP+1PO+1EO	0.0000001	0.60
			NP+2PO	0.0000000	0.66
NP+2PO+2EO	0.0000000	0.00
			NP+3PO+2EO	0.0000000	0.00
NP+1PC	0.0000000	0.02

Also show by Study on degradation, during degraded propoxylation phenol or alkyl phenol non-degradable be the estrogen active material. Be not limited to any concrete theory, we believe, the propylene oxide degraded of branching that directly is attached to the phenol ring is very slow, and ring itself can preferentially degrade, and do not stay any residual alkyl phenol. Study on degradation has been proved conclusively this approach.

Embodiment 2 uses the synthetic n nonylphenol+1PO+2EO of propylene carbonate

Utilize potassium carbonate catalyst, make 122.5g propylene carbonate (1.18M) and the reaction of 234.5g nonyl phenol. By NMR and gas-chromatography (GC) this is analyzed, find to contain less than the free nonyl phenol of 0.02 % by weight with greater than the secondary hydroxyl of 99.8 % by weight, this shows that all terminal hydroxyls of nonyl phenol all react basically. Use then 94.2g (21.4 moles) ethylene oxide to carry out ethoxylation. Utilize the afore-mentioned test program to test the estrogen of this product (that is, having the nonyl phenol alcoxylates of 1 mole of PO and 2 moles of EO subsequently), find that it does not have estrogen. Also show by Study on degradation, during degraded this material non-degradable be the estrogen active material.

The derivative that has been found that structure I I can be applicable to comprise in many industrial process of intensified oil reduction. Can prepare these products, can enduring high-concentration electrolyte and the surfactant of high temperature to provide. For example, have been found that surfactant (wherein, the R of structure I I₁=C9～C12 alkyl, R₂=H, C9～C12 alkyl, x=1, y=4～15, z=1, M=H or SO₃A, A=Na and Q=SO₃) extremely effective as the surfactant that is used for intensified oil reduction (EOR). Particularly, the product that has been found that M=H wherein contains aspect the aqueous solution of this surfactant and the interfacial tension between the crude oil (IFT) extremely effective in reduction, and the surfactant that uses as few as 0.05 % by weight can be brought down below 10 with this interfacial tension^-2The value of mN/m. Have been found that IFT is brought down below 10^-2The value of mN/m can improve capillary number 3～4 orders of magnitude, and overcomes the capillary pressure in the micro-hole of reservoir matrix (reservoir matrix), can permeate and replace oil so that inject fluid. Have been found that and contain 1 mole of PO and sulphonic acid ester and the sulfate derivative of EO more than 4 moles subsequently has high salt tolerance, can surpass the solution that forms clarification in the salt solution of 200,000PPM total dissolved solidss (TDS) containing. Corresponding sulfonate derivatives is salt water resistance extremely not only, can also use surpassing under 150 ℃ the temperature.

Embodiment 3

Lower Table II shown, compares with add 1 mole of propylene carbonate in nonyl phenol, by add the distribution of the nonyl phenol homologue that various amount PO obtain in nonyl phenol. Note that all products that prepare for utilizing the PO propoxylation, the distribution of PO homologue is all wider. Use the product (NP+1PC) of propylene carbonate preparation only to have the not propenoxylated nonyl phenol of 0.017 % by weight and 1 mole of PO adduct of 99.98 % by weight.

The Table II homologue distributes

PO	NP+1PC	NP+1.5PO	NP+2.5PO	NP+3.5PO
					0	0.017％	2％	1％	0.5％
1	99.98％	52.5％	10.3％	0.3％
					2		7.8％	25.6％	22.4％
3			12.2％	33.9％
					4			4.3％	25.7％
5			8.2％	10.5％
					6				5.7％

Embodiment 4NMR analyzes

The amount of the NP+1.5PO of residual not ethoxylation behind the EO of the different amounts of present embodiment demonstration adding. Even note that after adding 10 moles of EO, still have 3% secondary hydroxyl, described secondary hydroxyl represents terminal PO group.

The NMR of Table III primary hydroxyl and secondary hydroxyl analyzes

	Uncle %	Secondary %
			NP+1.5PO	＜2	＞98
NP+1.5PO+4EO	82	18
			NP+1.5PO+5EO	88	12
NP+1.5PO+6EO	91	9
			NP+1.5PO+10EO	97	3

The application of embodiment 5 in oil recovery

The explanation of this example can be used one of many application of composition of the present invention.The surfactant dissolves of one or more structure I I in water, synthetic salt solution or oil-field brine, and is injected into underground reservoir by one or more injection wells.Oil is contacted with injecting fluid, and from one or more recovery wells, recover the oil.Injecting well can be identical with recovery well, also can be the well that is different from recovery well.

As known in the art, can add other composition to injecting fluid.Comprising: tackifier include but not limited to polyacrylamide, xanthan gum and viscoelastic surfactant; Solvent includes but not limited to low-molecular-weight alcohol, two pure and mild alcohol ethers; Cosurfactant is as nonionogenic tenside, anion surfactant, amphoterics and cats product; Alkali includes but not limited to borate, silicate, carbonate, phosphoric acid salt, oxyhydroxide; Absorption reduces agent, includes but not limited to polyvinylpyrrolidone, polyethylene polymer, polyglucoside, Sulfite lignin, inorganic salt.

Embodiment 6 heavy oil are carried

Another example that product of the present invention is used is to be used in the conveying of heavy crude.Can the defined product emulsified crude oil of utilization structure II, in described product, can change the amount of the ethoxylation after adding 1 mole of PO and be combined in alkyl on the ring, so that required emulsifying stability to be provided.The emulsion of water, crude oil and tensio-active agent can be passed through pipe-line transportation, and " same as before " as fuel source, also oil can be separated from water and further refining.

Though described the present invention in conjunction with preferred implementation, but this is not intended to limit the scope of the invention to described specific form, on the contrary, its purpose is to contain following variation, change and equivalent way, and described variation, change and equivalent way are included in as defined by the appended claims in the spirit and scope of the present invention.

Claims (11)

1. the non-oestrogenic hormon phenol of a following structure and the preparation method of alkylphenol compound:

Wherein:

R and R ₁Separately separately and independently=H, C1～C24 straight chain or the alkyl of branching or the alkylidene group of C2～C24 straight chain or branching,

x＝1，

y＝1～30，

z＝0～30，

M＝H、SO ₃A、SO ₄A、COOA、PO ₄A，

M=H, Na, K, NH ₄, amine, Ca, Mg,

Q=SO ₃Or C1～C30 alkyl sulphonyl, and,

a＝0～2，

N=2 or greater than 2,

Described method is passed through wherein R and R ₁Separately separately and independently=phenol or the alkylphenol precursor of the structure I of the alkyl of H, C1～C24 straight chain or branching or the alkylidene group of C2～C24 straight chain or branching

Structure I

With the Texacar PC reaction, to form 1 mole of propenoxylated adducts, further then ethoxylation and/or propoxylation, subsequent transformation is required derivative.

2. the preparation method of non-oestrogenic hormon phenol as claimed in claim 1 and alkylphenol derivative, wherein, described required derivative is 2 moles or more than the condensation product of 2 moles of structure I and formaldehyde.

3. method of from subsurface reservoir, recovering the oil: inject the oil recovery composition that comprises following compositions by following manner:

A) one or more have the non-oestrogenic hormon phenol or the alkylphenol compound of following structure

Wherein:

R and R ₁Separately separately and independently=H, C1～C24 straight chain or the alkyl of branching or the alkylidene group of C2～C24 straight chain or branching,

x＝1，

y＝1～30，

z＝0～30，

M＝H、SO ₃A、SO ₄A、COOA、PO ₄A，

A=H, Na, K, NH ₄, amine, Ca, Mg,

Q=SO ₃Or C1～C30 alkyl sulphonyl, and,

a＝0～2，

N=2 or greater than 2,

B) optional one or more cosurfactants,

C) optional one or more cosolvent,

D) optional one or more tackifier,

E) optional one or more alkali,

F) optionally one or more absorption reduce agent,

G) salt solution,

With described optional component as known in the art, inject the solution of described oil recovery compositions and aqueous carrier by one or more injection wells to one or more underground reservoirs, make and inject fluid and contact with oily, and by one or more recovery wells oil recoveries.

4. the method for oil recovery as claimed in claim 3, wherein, described optionally one or more cosurfactants are selected from down group: anion surfactant, nonionogenic tenside, amphoterics.

5. the method for oil recovery as claimed in claim 3, wherein, described optionally one or more cosolvent are selected from down group: alcohol ether, two pure and mild alcohol.

6. the method for oil recovery as claimed in claim 3, wherein, described optionally one or more tackifier are selected from down group: polyacrylamide, viscoelastic surfactant, xanthan gum.

7. the method for oil recovery as claimed in claim 3, wherein, described optionally one or more alkali are selected from down group: borate, silicate, carbonate, phosphoric acid salt, oxyhydroxide.

8. the method for oil recovery as claimed in claim 3, wherein, described optionally one or more absorption reduce agent and are selected from down group: polyvinylpyrrolidone, polyoxyethylene glycol, gather alkyl glucoside, Sulfite lignin, inorganic salt.

9. the method for oil recovery as claimed in claim 3, wherein, described salt solution is selected from down group: water, synthetic salt solution, the water of generation, seawater.

10. the method for oil recovery as claimed in claim 3, wherein, described injection well is identical well or different wells with recovery well.

11. method of carrying heavy oil by following manner: utilize oil, water and have the aqueous solution formation emulsion of the tensio-active agent of following structure

Wherein:

R and R ₁Separately separately and independently=H, C1～C24 straight chain or the alkyl of branching or the alkylidene group of C2～C24 straight chain or branching,

x＝1，

y＝1～30，

z＝0～30，

M＝H、SO ₃A、SO ₄A、COOA、PO ₄A，

A=H, Na, K, NH ₄, amine, Ca, Mg,

Q=SO ₃Or C1～C30 alkyl sulphonyl, and,

a＝0～2，

N=2 or greater than 2.

Images