CN102485771A - Fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate and preparation and application thereof - Google Patents

Abstract

The invention relates to fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate and preparation and application thereof; the fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate has the following structural general formula: RO_n(EO)_mCH₂COOX, R represents aliphatic hydrocarbyl or alkylphenyl; (PO) n represents polyoxypropylene, n-6-12, (EO)_mThe polyoxyethylene fatty alcohol carboxylate surfactant is suitable for application in tertiary oil recovery by adding polyoxypropylene under the condition that the existing fatty alcohol raw material is not changed, the lipophilicity of fatty alcohol carboxylate surfactants is increased by adding the polyoxypropylene, the hydrophilic property can be adjusted by adding a small amount of polyoxyethylene, and the carboxylation of fatty alcohol polyoxypropylene ether can be realized at the same time.

Description

Fatty alcohol polyoxypropylene polyethenoxy ether carboxylate and preparation thereof and application

Technical field

The present invention relates to the AS field, particularly relate to a kind of fatty alcohol polyoxypropylene polyethenoxy ether carboxylate and preparation and application.

Background technology

Fatty Alcohol Ether Carboxylate is one type of novel AS, is by the nonionogenic tenside modification, has characteristics such as surface tension is low, toxicity is little, readily biodegradable, is one type multi-functional " green surfactant ".Because its special nature, Fatty Alcohol Ether Carboxylate is fallen field such as glutinous at makeup, washing composition, biological chemistry, pharmacy, food-processing, crude oil demulsification, viscous crude and is had a wide range of applications.At present, Fatty Alcohol Ether Carboxylate class tensio-active agent has been carried out systematically research abroad, and had tandem product to produce in batches, output increases year by year.And domestic though product for trial sale arranged, kind and output are less, still are in the starting stage.

Aliphatic alcohol polyethenoxy ether carboxylate is that application is the most a kind of in the Fatty Alcohol Ether Carboxylate.It is similar with soap on chemical structure, and different is between hydrophobic group and hydrophilic group, to have added the ethylene oxide chain with certain adduction number, thereby makes it have many premium propertiess of negatively charged ion and nonionogenic tenside.And the surface property of product can be regulated through the length that changes carbochain, adduction number and the pH value of EO, and wherein the acid product is the nonionic characteristic, and neutral salt formula product then is an anion characteristic fully.But as the tensio-active agent that uses in the TOR; Conventional aliphatic alcohol polyethenoxy ether carboxylate wetting ability is too strong; Even its hydrophilic group Soxylat A 25-7 segment is foreshortened to one, two polymerization degree; Obtain being fit to the used tensio-active agent of TOR, the length of its hydrophobic group segment Fatty Alcohol(C12-C14 and C12-C18) also need be adjusted between the 30-40 accordingly, and this is for the unusual difficulty selected for use beyond doubt of Fatty Alcohol(C12-C14 and C12-C18).

Summary of the invention

The purpose of this invention is to provide a kind of fatty alcohol polyoxypropylene polyethenoxy ether carboxylate; Keeping under the constant situation of existing hydrophobic group Fatty Alcohol(C12-C14 and C12-C18); Make it have long carbochain hydrophobic structure through adding the propylene oxide segment; And can be through regulating polyoxypropylene, the length of T 46155 copolymerization section is synthesized the series of surfactants with different interfacial characteristicses, thereby obtains being fit to the used tensio-active agent of TOR.

The fatty alcohol polyoxypropylene polyethenoxy ether carboxylate has following general structure: RO (PO)_n(EO)_mCH₂COOX, R represent aliphatic group or alkyl phenyl; (PO)_nRepresent polyoxypropylene, n=6-12, (EO)_mRepresent T 46155, m=1-4, X represents basic metal.

Aliphatic group or alkyl phenyl that it is 8-22 that said R represents total C number.

Said n is 8-10.

Said m is 1-3.

Said X is potassium or sodium.

Said R is C₁₆-C₁₈Alkyl, said X are potassium.

The surfactant structure of the present invention's design, the Fatty Alcohol(C12-C14 and C12-C18) and the polyoxypropylene of left end are oleophilic group, and the T 46155 and the carboxyl of right-hand member are hydrophilic group.Having now under the constant situation of Fatty Alcohol(C12-C14 and C12-C18) raw material, mainly be to strengthen the oleophilicity of Fatty Alcohol(C12-C14 and C12-C18) carboxylate surface active agent class, thereby satisfy the TOR needs through introducing the polyoxypropylene segment.Surfactant structure adds a spot of T 46155 can regulate its hydrophilicity, can realize the carboxylic acidization of fatty alcohol polyoxypropylene ether simultaneously.

The preparation method of fatty alcohol polyoxypropylene polyethenoxy ether carboxylate, adopt following steps:

(1) ROH and propylene oxide reaction generate RO (PO)_nH;

(2) RO (PO)_nH and reacting ethylene oxide generate RO (PO)_n(EO)_mH;

(3) RO (PO)_n(EO)_mH adopts the carboxymethylation method to generate RO (PO)_n(EO)_mCH₂COOX.

The concrete operation method of said step (3) is: (A), with RO (PO)_n(EO)_mH and XOH reaction, (B), in the reaction product of (A), add the Monochloro Acetic Acid reaction and accomplish and get final product.

Said mol ratio RO (PO)_n(EO)_mH: XOH: Monochloro Acetic Acid=1: 2.5: 2.

Said (A) goes on foot to gather for 40-80 ℃ and reacted 1-3 hour down.

Said (B) step is 40-80 ℃ and reacted 5-10 hour down.

Said (A) step is 60 ℃ reacted 2 hours down, and said (B) step is 60 ℃ and reacted 8 hours down.

The application of fatty alcohol polyoxypropylene polyethenoxy ether carboxylate in TOR.

The synthetic route of Fatty Alcohol Ether Carboxylate is as shown in Figure 7:

1. the fatty alcohol polyoxypropylene Soxylat A 25-7 is synthetic

The polyoxypropylene ethers tensio-active agent of propylene oxide and reactive hydrogen addition, its reaction are gradual reactions, generate the product of different polymerization degree, and the content of title product is higher in the wherein narrow distribution product.The target of this experiment is that the synthetic product polymerization degree is the fatty alcohol polyoxypropylene Soxylat A 25-7 of narrow distribution, because catalyzer alkalescence is high more, the purpose product yield is high more, so select for use Pottasium Hydroxide as catalyst for reaction.

The alkylation reaction that Fatty Alcohol(C12-C14 and C12-C18) and propylene oxide took place can be divided into two stages, and the fs is obtained the hydroxyethylation compound by the functional group of alkanisation and a part propylene oxide reaction, and this is typical alkylation reaction.Reaction equation is following:

The subordinate phase of reaction is the hydroxyethyl thing of generation and the oligomerisation reaction of propylene oxide, or claims the polyethers reaction.Reaction equation is following:

Can confirm the add-on of propylene oxide according to the needs of the polymerization degree.

After fatty alcohol polyoxypropylene ether is synthetic, adds oxyethane and continue reaction generation fatty alcohol polyoxypropylene Soxylat A 25-7, its reaction equation is following:

Can confirm the add-on of oxyethane according to the needs of the polymerization degree.

In the design of structural formula of the present invention, mainly be to want through introducing the oleophilicity that the polyoxypropylene segment strengthens Fatty Alcohol(C12-C14 and C12-C18) carboxylate surface active agent class, satisfying the TOR needs, so the polymerization degree of propylene oxide is controlled at 6-12.Surfactant structure adds a spot of T 46155 can regulate its hydrophilicity, can realize the carboxylic acidization of fatty alcohol polyoxypropylene ether simultaneously, therefore can reduce the polyoxyethylated polymerization degree to 1-4 as far as possible.Finally obtain tensio-active agent required for the present invention.

2. Fatty Alcohol Ether Carboxylate is synthetic

The carboxymethylation method is the technological line that under alkaline condition, directly reacts with fatty alcohol-ether with Monochloro Acetic Acid or its salt.Fatty alcohol-ether forms negative oxygen ion in the alkaline purification process, in the carboxymethylation process, Mono Chloro Acetic Acid is carried out nucleophilic substitution then, and the active site negative oxygen ion that forms in the alkaline purification process is many more, and good more to chloroacetic replacement effect, chloroacetic utilization ratio is high more.

Its reaction equation is as follows:

Use aforesaid method, obtain C successively₁₈PO₉EO₂CH₂COOK, C₁₈PO₁₀EO₃CH₂COOK, C₁₆PO₈EO₂CH₂Fatty Alcohol Ether Carboxylate tensio-active agents such as COOK.Through the oil water interfacial tension test, this type of tensio-active agent can make oil water interfacial tension reach ultralow, thereby satisfies the TOR needs.

Description of drawings

Fig. 1: C₁₈PO₉EO₂The infrared spectrum of H

Fig. 2: C₁₈PO₁₀EO₃The infrared spectrum of H

Fig. 3: C₁₆PO₈EO₂The infrared spectrum of H

Fig. 4: C₁₈PO₉EO_2CH₂The infrared spectrum of COOK

Fig. 5: C₁₈PO₁₀EO₃CH₂The infrared spectrum of COOK

Fig. 6: C₁₆PO₈EO₂CH₂The infrared spectrum of COOK

The synthetic route synoptic diagram of Fig. 7 Fatty Alcohol Ether Carboxylate

Embodiment

Embodiment 1

Synthetic compound

1. the building-up reactions of fatty alcohol polyoxypropylene Soxylat A 25-7

The Fatty Alcohol(C12-C14 and C12-C18) here can be straight chain or side chain for the C length overall is 8～22 Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol, preferred straight chain, and the form through proportioning raw materials obtains that required PO is long to be grown with EO.

In autoclave, add a certain amount of Fatty Alcohol(C12-C14 and C12-C18) and pulverous Pottasium Hydroxide, stir, feed N when being warming up to 50～60 ℃₂Do protection gas, continue to be warming up to about 120 ℃.At N₂Protection adds down propylene oxide, and the reinforced time is two hours, is warming up to 140 ℃ after adding material, and isothermal reaction two hours naturally cools to room temperature, and reaction obtains fatty alcohol polyoxypropylene ether.

In autoclave, add a certain amount of fatty alcohol polyoxypropylene ether and pulverous Pottasium Hydroxide.Stir, feed N when being warming up to 50～60 ℃₂Do protection gas, continue to be warming up to about 120 ℃.Then at N₂Do under the condition of protection gas and add oxyethane, the reinforced time is one hour, is warming up to 130 ℃ after adding material, and isothermal reaction two hours naturally cools to room temperature, and reaction obtains the fatty alcohol polyoxypropylene Soxylat A 25-7.

As one of them compound that utilizes above-mentioned building-up reactions, the present invention to obtain is C₁₈PO₉EO₂H.Fig. 1 is its infrared spectrogram, as can be seen from the figure, and at 3400cm^-1The place is the stretching vibration of O-H; At 2962cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2872cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2926cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2853cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1150cm^-1The place is the stretching vibration of C-O.

Another compound of the present invention is C₁₈PO₁₀EO₃H, its infrared figure is Fig. 2, as can be seen from the figure, at 3420cm^-1The place is the stretching vibration of O-H; At 2968cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2882cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2926cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2843cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1140cm^-1The place is the stretching vibration of C-O.

Another compound of the present invention is C₁₆PO₈EO₂H, its infrared figure is Fig. 3, as can be seen from the figure, at 3410cm^-1The place is the stretching vibration of O-H; At 2978cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2892cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2926cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2833cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1140cm^-1The place is the stretching vibration of C-O.

2. Fatty Alcohol Ether Carboxylate is synthetic

N (fatty alcohol-ether): n (Pottasium Hydroxide): n (Mono Chloro Acetic Acid)=1: 2.5: 2

In flask, add fatty alcohol polyoxypropylene Soxylat A 25-7 and pulverous Pottasium Hydroxide, reaction is two hours in the time of 60 ℃, under this temperature, adds Mono Chloro Acetic Acid then, continues reaction and gets final product in eight hours.

Overnight, remove the water that generates in the reaction process, refluxed about 4 hours to wherein adding absolute ethyl alcohol, suction filtration with its rotary evaporation, can obtain flaxen paste solid, and this product is thick Fatty Alcohol Ether Carboxylate.

Thick Fatty Alcohol Ether Carboxylate is dissolved in ethanol: in the solution of water (7: 3); Transfer in the separating funnel of 500mL, add a certain amount of sherwood oil, thermal agitation; Standing demix; The upper strata is the unreacting material of petroleum ether dissolution, and lower floor is the product of dissolve with ethanol solution, it is revolved steaming can obtain purer Fatty Alcohol Ether Carboxylate.

Phase fixes with column chromatography silica gel (0.154～0.076mm particle diameter); With the sample dissolution after handling in the ethanolic soln of heat; Carry out wash-out with 4: 1 acetone and sherwood oil mixing solutions as moving phase; With each eluate distill, dry, weigh, and the productive rate that calculates following three kinds of products is respectively C₁₈PO₉EO₂CH₂COOK:78.95%; C₁₈PO₁₀EO₃CH₂COOK:82.36%; C₁₆PO₈EO₂CH₂COOK:80.14%.

With hamming 1622 is titrating solution, and thymolsulfonphthalein and methylene blue are indicator, and methylene dichloride is respectively C for dividing phase solvent through the molecular weight of measuring and calculate following three kinds of products₁₈PO₉EO₂CH₂COOK:970.03; C₁₈PO₁₀EO₃CH₂COOK:1071.56; C₁₆PO₈EO₂CH₂COOK:886.32.

The synthetic C that obtains of the inventive method₁₈PO₉EO₂CH₂The infrared spectrum of COOK is as shown in Figure 4.As can be seen from the figure, at 2960cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2868cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2920cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2848cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1130cm^-1The place is the stretching vibration of C-O; Compare withraw material spectrogram 1, this spectrogram is at 1620cm^-1The C=O charateristic avsorption band appears in the place, shows synthetic title product.

The synthetic C that obtains of the inventive method₁₈PO₁₀EO₃CH₂The infrared spectrum of COOK is as shown in Figure 5.As can be seen from the figure, at 2980cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2878cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2910cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2828cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1150cm^-1The place is the stretching vibration of C-O; Compare with raw material spectrogram 2, this spectrogram is at 1610cm^-1The C=O charateristic avsorption band appears in the place, shows synthetic title product.

The synthetic C that obtains of the inventive method₁₆PO₈EO₂CH₂The infrared spectrum of COOK is as shown in Figure 6.As can be seen from the figure, at 2982cm^-1The place is CH₃The asymmetrical stretching vibration of C-H; 2878cm^-1The place is CH₃The symmetrical stretching vibration of C-H; 2920cm^-1The place is CH₂The asymmetrical stretching vibration of C-H; 2828cm^-1The place is CH₂The symmetrical stretching vibration of C-H; 1150cm^-1The place is the stretching vibration of C-O; Compare with raw material spectrogram 3, this spectrogram is at 1610cm^-1The C=O charateristic avsorption band appears in the place, shows synthetic title product.

Embodiment 2

Application in TOR

Select U.S. Texas-500 type interfacial tensimeter for use, revolve the method for dripping and measure IT.The crude oil of surveying is Kelamayi, Xinjiang crude oil.

Table 1:C₁₆PO₈EO₂CH₂The IT value of COOK under different weak base concentration

Table 2:C₁₈PO₁₀EO₃CH₂The IT value of COOK under different weak base concentration

Table 1 is 0.3% C₁₆PO₈EO₂CH₂COOK is at different weak base (Na₂CO₃) IT under the concentration in crude oil.At Na₂CO₃Be 0.2%～0.4% o'clock, this tensio-active agent reaches a ultralow IT value very soon.

Table 2 is 0.3% C₁₈PO₁₀EO₃CH₂COOK is at different weak base (Na₂CO₃) under the concentration in the IT value of crude oil, at Na₂CO₃Concentration is than relative superiority or inferiority, and this tensio-active agent reaches a ultralow IT very soon.

Embodiment 3

Carry out the evaluation of weak base combination flooding oil displacement efficiency at the natural exposure rock core of the long 30cm of indoor selection, diameter 3.8cm.The tensio-active agent of weak base compound system adopts the C among the embodiment (2)₁₆PO₈EO₂CH₂COOK and C₁₈PO₁₀EO₃CH₂COOK, polymkeric substance adopt 2,500 ten thousand SEPIGEL 305 HPAM, and crude oil is the Xinjiang dewatered oil.

The oil displacement experiment result sees table 3.The weak base composite displacement system improves the RF amplitude at 21.5%-22.3%.The laboratory core oil displacement experiment shows that this displacing surfactant system has the ability of good raising crude oil oil displacement efficiency.

Table 3 weak base composite displacement system laboratory core oil displacement efficiency evaluation experimental result

Claims (9)

1. a fatty alcohol polyoxypropylene polyethenoxy ether carboxylate is characterized in that: have following general structure: RO (PO)_n(EO)_mCH₂COOX, R represent aliphatic group or alkyl phenyl; (PO)_nRepresent polyoxypropylene, n=6-12, (EO)_mRepresent T 46155, m=1-4, X represents basic metal.

2. fatty alcohol polyoxypropylene polyethenoxy ether carboxylate according to claim 1 is characterized in that: aliphatic group or alkyl phenyl that it is 8-22 that the said R of general structure represents total C number.

3. fatty alcohol polyoxypropylene polyethenoxy ether carboxylate according to claim 1 is characterized in that: the said n of general structure is 8-10, and said m is 1-3, and said X is potassium or sodium.

4. fatty alcohol polyoxypropylene polyethenoxy ether carboxylate according to claim 1 is characterized in that: the said R of general structure is C₁₆-C₁₈Alkyl, said X are potassium.

5. the preparation method of the described polyoxyethylene polyoxypropylene ether carboxylate of claim 1 is characterized in that: adopt following steps:

(1) ROH and propylene oxide reaction generate RO (PO)_nH;

(2) RO (PO)_nH and reacting ethylene oxide generate RO (PO)_n(EO)_mH;

(3) RO (PO)_n(EO)_mH adopts the carboxymethylation method to generate RO (PO)_n(EO)_mCH₂COOX.

6. the preparation method of polyoxyethylene polyoxypropylene ether carboxylate according to claim 5 is characterized in that: the concrete operation method of said step (3) is: (A), with RO (PO)_n(EO)_mH and XOH reaction, (B), in the reaction product of (A), add the Monochloro Acetic Acid reaction and accomplish and get final product; RO (PO) in molar ratio_n(EO)_mH: XOH: Monochloro Acetic Acid is 1: 2.5: 2.

7. the preparation method of polyoxyethylene polyoxypropylene ether carboxylate according to claim 6, said (A) go on foot to gather for 40-80 ℃ and reacted 1-3 hour down, and said (B) step is 40-80 ℃ and reacted 5-10 hour down.

8. the preparation method of polyoxyethylene polyoxypropylene ether carboxylate according to claim 7 is characterized in that: said (A) step is 60 ℃ reacted 2 hours down, and said (B) step is 60 ℃ and reacted 8 hours down.

9. the application of the described fatty alcohol polyoxypropylene polyethenoxy ether carboxylate of claim 1 is characterized in that: be used for TOR as tensio-active agent.

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