WO 2009/122438 Al

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property OrganizationInternational Bureau

(10) International Publication Number(43) International Publication Date

8 October 2009 (08.10.2009) WO 2009/122438 Al

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for everyCIlC 1/00 (2006.01) C07C 17/093 (2006.01) kind of national protection available): AE, AG, AL, AM,

AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ,(21) International Application Number: CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ,

PCT/IN2009/000205 EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,

(22) International Filing Date: HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR,

26 March 2009 (26.03.2009) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,

(25) Filing Language: English NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG,

(26) Publication Language: English SK, SL, SM, ST, SV, SY, TJ, TM, TN, TR, TT, TZ, UA,UG, US, UZ, VC, VN, ZA, ZM, ZW.

(30) Priority Data:719/MUM/2008 3 1 March 2008 (3 1.03.2008) IN (84) Designated States (unless otherwise indicated, for every

kind of regional protection available): ARIPO (BW, GH,(71) Applicant (for all designated States except US): GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,

ADITYA BIRLA SCIENCE & TECHNOLOGY CO. ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ,LIMITED [IN/IN]; Aditya Birla Centre, S.K., Ahire TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE,Marg, Worli, Mumbai 400 025, Maharashtra (IN). ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,

MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, TR),(72) Inventors; and

OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML,(75) Inventors/Applicants (for US only): SATAM, Rasika

MR, NE, SN, TD, TG).[IN/IN]; A-304 Sankalpsiddhi Co-Op, HSL, S.B. Marg,Matunga Road, (West), Mumbai 400 016 (IN). BO- Declarations under Rule 4.17:ROLE, YOgesh [IN/IN]; 39, Jainnagar, Kanchanganga

— as to the identity of the inventor (Rule 4.17(if)Appt, Jalgaon 425 002, Maharashtra (IN). MANDAL,Sisir, Kumar [IN/IN]; 1-102, Awho Complex, Dara En — of inventorship (Rule 4.1 7(ivf)clave, Sector 9, Nerul, Navi, Mumbai 400 706 (IN).

Published:NIPHADE, Amol [IN/IN]; 402 Sheetal Building, NearBedekar Hospital, Naupada, Thane (West) 400 602, M a — with international search report (Art. 21(3))harashtra (IN). — before the expiration of the time limit for amending the

(74) Agent: MOHAN, Dewan; R.K. DEWAN & COMPANY, claims and to be republished in the event of receipt of

Podar Chambers, S.A . Brelvi Road, Fort, Mumbai 400 amendments (Rule 48.2(h))

001 (IN).

(54) Title: IMPROVED PROCESS FOR HEAT STABLE CHLORINATED PARAFFIN WAX

(57) Abstract: A method for synthesis of chlorinated paraffin, the method comprising reacting a Cs-24 paraffinic hydrocarbon withchlorine gas in the presence of 100 to 1500 ppm of an stabilizer at a temperature in the range of 25 C to 200 C and at a pressure inthe range of 1 to 3 atmospheres.

IMPROVED PROCESS FOR HEAT STABLE CHLORINATED

PARAFFIN WAX

FIELD OF THE INVENTION

The invention relates to a method for synthesis of chlorinated paraffin. The

invention also relates to the chlorinated paraffin and to the compositions

thereof.

BACKGROUND OF THE INVENTION

Chlorinated paraffins are widely used in plasticizers and flame retardant

formulations. They are also used in formulations having applications as

additives in metal working fluids, in sealants, paints and coatings. Paraffins

are usually chlorinated with chlorine gas in a jacketed reactor provided with a

coolant liquid. To improve the productivity of the chloroparaffin products,

high reactivity of the paraffin with chlorine gas and high thermal stability of

the chloroparaffin product are desired. During conventional chlorination

methods, however, the reactivity of paraffins with chlorine gas is limited.

Further, the chloroparaffin products are usually thermally unstable and would

undergo decomposition by the elimination of hydrogen chloride. Various

methods are known wherein stabilizing compounds are used to improve the

heat stability of the chloroparaffin product. US patent 2722557 discloses a

method for paraffin chlorination in the presence of a glycolic stabilizer.

However, when glycols are used, the overall chlorine content of the

chloroparaffin product is reduced, which is not desirable. US patent 3284519

discloses a method wherein diazo carboxylate is used as a stabilizer for

increasing the thermal stability of chloro paraffin product. Diazo carboxylate

is, however, not environmentally benign and is therefore not recommended.

There is a need for a synthetic method to obtain thermally stable

chloroparaffin without the above mentioned disadvantages.

OBJECTS OF THE INVENTION

An object of the invention is to provide a method for synthesis of chlorinated

paraffins wherein the reactivity of chlorine gas with paraffins and the thermal

stability of the chloroparaffin product are improved.

Another object of the invention is to provide thermally stable chlorinated

paraffin suitable for a wide range of applications.

A further object of the invention is to provide compositions comprising

thermally stable chlorinated paraffins.

SUMMARY OF THE INVENTION

The invention is based on the finding that when an activity control agent

selected from organo tin compounds and mercaptides, carboxylates, sulfides

and maleates of a group II and a group 14 metal is used in paraffin

chlorination reactions, the chlorination reactivity and thermal stability of the

chloroparaffin product are significantly increased. The improvement in

chlorination reactivity and in the thermal stability of the product is

advantageous in increasing the productivity and reducing the cost of

synthesis.

In accordance with the present invention, there is provided a method for

synthesis of chlorinated paraffin, the method comprising reacting a C8-24

paraffmic hydrocarbon with chlorine gas in the presence of 100 to 1500 ppm

of an activity control agent at a temperature in the range of 25°C to 2000C

and at a pressure in the range of 1 to 3 atmospheres.

Typically, the hydrocarbon is preheated at a temperature in the range of 500C

to 800C.

Typically, the activity control agent is selected from a group consisting of an

organo tin compound and mercaptides, carboxylates, sulfides and maleates of

a group II and a group 14 metal.

Typically, the group II metal is selected from calcium and barium and the

group 14 metal is selected from tin and lead

Typically, the activity control agent is an alkyl mercaptide.

Typically, the reaction is carried out in the presence of 100 to 1500 ppm of

activity control agent.

Typically, the reaction is carried out at a temperature in the range of 600C to

1500C.

Typically, chlorinated paraffin is synthesized by the method of the present

invention.

Typically, a composition comprising the chlorinated paraffin is disclosed.

DETAILED DESCRIPTION OF THE INVENTION

Accordingly, the invention provides a method for synthesis of chloroparaffin

products wherein an activity control agent is used.

The following terms, wherever used in the description herein and in the

appended claims, have the meaning defined below.

The term normalparaffin refers to paraffin having the characteristics as given

in table 1.

Table 1: Characteristics of normal paraffin

The term light normal paraffin refers to paraffin having characteristics as

given in table 2:

Table 2: Characteristics of light normal paraffin

The term raw paraffin refers to a mixture of normal paraffin and light normal

paraffin.

The term activity control agent refers to any additive, accelerator, promoter

or catalyst that when used in the paraffin chlorination reaction at least

improves the heat stability of the chloroparaffin product and increases the

reaction rate.

In one embodiment, the invention provides a method for synthesis of a

chlorinated paraffin, the method comprising reacting a C8-24 paraffinic

hydrocarbon with chlorine gas in the presence of 100 to 1500 ppm of an

activity control agent at a temperature in the range of 25°C to 2000C and at a

pressure in the range of 1 to 3 atmospheres.

In another embodiment, the invention provides a method for synthesis of a

chlorinated paraffin, the method comprising reacting a C g-24 paraffinic


activity control agent at a temperature in the range of 250C to 2000C and at a

pressure in the range of 1 to 3 atmospheres wherein the activity control agent

is selected from a group consisting of an organo tin compound and

mercaptides, carboxylates, sulfides and maleates of a group II and a group 14

metal.






is selected from a group consisting of an organo tin compound and

mercaptides, carboxylates, sulfides and maleates of a group II and a group 14

metal and the hydrocarbon is preheated at a temperature in the range of 500C

to 800C.





pressure in the range of 1 to 3 atmospheres wherein the group II metal is

selected from calcium and barium and the group 14 metal is selected from tin

and lead.






is an alkyl mercaptide.






In another embodiment, the invention provides a method for synthesis of



activity control agent at a temperature in the range of 600C to 1500C and at a


In yet another embodiment, the invention provides chlorinated paraffin

synthesized by reacting a C8-24 paraffinic hydrocarbon with chlorine gas in

the presence of 100 to 1500 ppm of an activity control agent at a temperature

in the range of 25°C to 2000C and at a pressure in the range of 1 to 3

atmospheres.

In a further embodiment, the invention provides a composition comprising

chlorinated paraffin synthesized by reacting a C8-24 paraffinic hydrocarbon

with chlorine gas in the presence of 100 to 1500 ppm of an activity control

agent at a temperature in the range of 250C to 2000C and at a pressure in the

range of 1 to 3 atmospheres.

The method of the invention provides chloroparaffin products having

relatively high thermal stability. The method is usually carried out in a

jacketed reactor provided with a coolant liquid for controlling the reactor

temperature and a pre-heater for heating the paraffin. Additionally, the

reactor can have an overhead gas-liquid separating arrangement and a gas

distribution arrangement. A glass reactor, a lead or a steel reactor can be used

for carrying out the method.

The paraffin feed used in the method of the invention can be a normal

paraffin, a light normal paraffin or a mixture of the two paraffins.

Advantageously, the paraffin is preheated to around 600C before chlorination

reaction. The chlorine gas used for the reaction can be obtained from a

membrane chlorine plant.

The activity control agent used in the method of the invention include organo

tin compounds and mercaptides, carboxylates, sulfides and maleates of a

group II and a group 14 metal. Advantageously, an alkyl tin mercaptide is

used as the activity control agent. The activity control agent is used in the

reaction in an amount ranging from 100 to 1500 ppm. Advantageously, 500

to 800 ppm of activity control agent is used.

The method of the invention is carried out at a temperature in the range of

25°C to 2000C and at a pressure in the range of 1 to 3 atmospheres.

Advantageously, the method is carried out at a temperature in the range of

6 O0C to 1200C and at a pressure of around 1 atmosphere.-

The invention also provides a chlorinated paraffin, having improved thermal

stability, and compositions thereof. The chloroparaffin compositions can be

used for various applications including metal working fluids, sealants, leather

processing, in paints and coatings, carbonless copy paper and as flame

retardants/softeners in rubbers, textiles, PVC and other polymers. The

composition can contain a single chloroparaffin or a mixture of different

chloroparaffins. Further, in addition to the chloroparaffin, the compositions

can contain solvents and additives that can impart special characteristics and

functionalities.

Apart from increasing rate of chlorination of the paraffins and yielding

chloroparaffin products having improved thermal stability, the method of the

invention could lead to considerable reduction in the formation of

carbonaceous and pitchy products. The method of the invention could also

reduce the amount of unreacted chlorine gas in the reactor, resulting in

operational and cost benefits. Typically, the method of the invention has a

batch cycle time reduced by 3 to 4 hrs as compared to the conventional

methods.

The invention is further illustrated by way of the following non limiting

examples.

In the examples and the results that follow, specific gravity and density of the

chloroparaffin product is determined by using a hydrometer. Weight loss

studies were performed by measuring loss in weight of final product after

heating at a temperature of 18O0C for half an hour. Heat test was conducted

by keeping a beaker containing the product in an oven at a temperature of

18O0C.

EXAMPLES

Example 1: Synthesis of chlorinated paraffin in the absence of activity

control agent

In a lead-lined reactor of 10 TON capacity, 2.4 TON normal paraffin

preheated to 600C was taken for chlorination. The reactor was equipped with

the cooling jacket, chlorine inlet sparger, off-gas outlet valve and temperature

sensors. Arrangements were made for direct supply of chlorine gas at 300C

from the membrane chlorine plant. The reaction temperature was controlled

with a combination of chlorine flow and cooling water-inlet flow. Off-gases

of the reaction were passed through the water scrubber for removal of HCl-

gas. The scrubber outlet was given to the caustic solution tank for converting

the un-reacted chlorine into sodium hypochlorite. Chlorination reaction was

run for 1400 minutes and the temperature was allowed to rise from 600C to

120 0C, more precisely from 700C to 1100C during the reaction. At the end of

1400 minutes the chlorine flow was stopped and air flow to remove the HCl

and trapped Cl was started. The air was passed for 2 hours, meanwhile the

reactor temperature dropped to 500C. At this temperature the product was

unloaded in the aeration tank; final aeration was done for 2 hr. 2 kg of epoxy

soya stabilizer per 250 kg of chloroparaffin product was added to the product.

Specific gravity was checked for analyzing the rate of reaction. Product

quality was checked by weight loss and heat heat stability. The synthetic

experiments carried out and the results obtained without the addition of any

activity control agent using different paraffin feeds are displayed against

experiment No.s 1 and 4 in table 3.

Example 2: Synthesis of chlorinated paraffin in the presence of activity

control agent

In a lead-lined reactor of 10 TON capacity, 2.4 TON normal paraffin and 12

g of butyl tin mercaptide (activity control agent), preheated to 600C was taken

for chlorination. The reactor was equipped with a cooling jacket, chlorine

inlet sparger, off-gas outlet valve and temperature sensors. Arrangements

were made for direct supply of chlorine gas at 300C from a membrane

chlorine plant. The reaction temperature was controlled with a combination

of chlorine flow and jacketed cooling water-inlet flow. Off-gases of the

reaction were passed through the water scrubber for removal of hydrogen

chloride gas. The scrubber outlet was given to the caustic solution tank for

converting the unreacted chlorine into sodium hypochlorite. Second lot of 12

g butyl tin mercaptide was added after one hour of FRR (Free Radical

Reaction). Chlorination reaction was run for 1400 minutes and the

temperature was allowed to rise from 600C to 1200C, more precisely from

700C to 1100C during the reaction. At the end of 1400 minutes the chlorine

flow was stopped and air flow to remove the HCl/ dissolved Cl2 was started.

The air was passed for 2 hours, meanwhile the reactor temperature dropped to

50 0C. At this temperature, the product was unloaded in the aeration tank and

final aeration was done for 2 hr. 2 kg of epoxy soya stabilizer per 250 kg of

chloroparaffin product was added, followed by 7kg butyl tin mercaptide to

the product for better heat stability. Specific gravity was measured for

analyzing the rate of reaction. Product quality was determined by weight loss

and heat heat stability. The results of the synthetic experiments carried out

under various conditions in the presence of the activity control agent are

given against Expt Nos 2, 3 and 5 in table 3.

The results of the various chlorination experiments using paraffins carried out

under various conditions are compared in table 3.

Table 3: Comparison of reactivity and heat stability of chloroparaffins

synthesized under various conditions

From table 3 it is clear that on following the method of the invention (as

exemplified by experiment Nos 2, 3 and 5), there is increased rate of

chlorination (as evidenced by the relatively less time required [1200 minutes

and 1370 minutes as against 1400 minutes] for reaching a specific gravity of

1.2 g/cm3) and increased heat stability of the chloroparaffin product (as

evidenced by the relatively less percentage weight loss[0.17 and 0.45 as

against 0.33 and 0.68 respectively] when subjected to a temperature of 1800C

for half an hour and also by the observed heat stability of. the product at

1800C).

The reactivity increase of paraffin chlorination reaction on following the

method of the invention is further evident from Fig 1 and Fig 3. Fig 1

displays the specific gravity profile of chloroparaffin product obtained by

chlorination of normal paraffin and Fig 3 displays the specific gravity profile

of chloroparaffin product obtained by chlorination of raw paraffin. From Fig

1 and Fig 3 it is clear that on following the method of the invention where an

activity control agent is used, chloroparaffin of desired specific gravity is

obtained at lower reaction times.

Fig 2 and Fig 4 display the appearance of chloroparaffin products obtained by

the chlorination of normal paraffin and raw paraffin respectively. In each of

the figures, the chloroparaffin product (The liquid in the beaker marked as B

and the liquid in the beaker marked as E) obtained on following the method

of the invention has better clarity. Better product clarity is indicative of less

contamination of the product by carbonaceous and pitchy by products, on

following the method of the invention. In other words, on following the

method of the invention, product selectivity and purity during paraffin

chlorination are improved. Therefore, the method of the invention ensures

maximum yield and minimizes the requirement of cumbersome purification

procedures.

TECHNICAL ADVANTAGES

In accordance with the present invention, the amount of unreacted chlorine is

reduced by at least 40% which was determined by the amount of calcium

carbonate required to neutralize the unreacted chlorine coming from the

reactor. Thus, the method in accordance with the present invention shows

increase in the reactivity of the chlorine and heat stability of the

chloroparraffin, which results in improvement of chloroparaffin productivity.

In accordance with the present invention, the improvement in thermal

stability of the chloroparaffin is beneficial in applications that require

operations at higher temperatures. Moreover, in accordance with the present

invention, the heat stability of the chloroparaffins reduces or even eliminates

the need for the addition of expensive external stabilizing agents, thereby

resulting in improvement in chloroparaffin purity and reduction in cost.

The method in accordance with the present invention allows better control of

the reaction kinetics that help in reducing run away reactions and 'flashing'

of the paraffins. The activity control agents used in the method in accordance

with present invention are less expensive and are added only in ppm

quantities to obtain the thermally stable chloroparaffins.

While considerable emphasis has been placed herein on the specific steps of

the preferred method, it will be appreciated that many steps can be made and

that many changes can be made in the preferred steps without departing from

the principles of the invention. These and other changes in the preferred steps

of the invention will be apparent to those skilled in the art from the disclosure

herein, whereby it is to be distinctly understood that the foregoing descriptive

matter is to be interpreted merely as illustrative of the invention and not as a

limitation.

Claims:

1. A method for synthesis of chlorinated paraffin, the method comprising

reacting a C8-24 paraffinic hydrocarbon with chlorine gas in the

presence of 100 to 1500 ppm of an activity control agent at a

temperature in the range of 250C to 2000C and at a pressure in the

range of 1 to 3 atmospheres.

2. The method as claimed in claim 1, wherein the hydrocarbon is

preheated at a temperature in the range of 500C to 800C.

3. The method as claimed in any one of the claims 1 or 2, wherein the

activity control agent is selected from a group consisting of an organo

tin compound and mercaptides, carboxylates, sulfides and maleates of

a group II and a group 14 metal.

4. The method as claimed in claim 3, wherein the group II metal is

selected from calcium and barium and the group 14 metal is selected

from tin and lead.

5. The method as claimed in any one of the claims 1 to 4, wherein the

activity control agent is an alkyl mercaptide.


reaction is carried out in the presence of 500 to 800 ppm of activity

control agent.


reaction is carried out at a temperature in the range of 600C to 1500C.

8. A chlorinated paraffin synthesized by the method as claimed in any

one of the claims 1 to 7.

9. A composition comprising the chlorinated paraffin as claimed in claim

8.

INTERNATIONAL SEARCH REPORT International application No

PCT/IN 2009/000205

A CLASSIFICATION OF SUBJECT MATTERIPC8: C11C 1/00 (2006.01); C07C 17/093 (2006.01)According to International Patent Classification (IPC) or to both national classification and IPC

B FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols)

IPC8: C11C; C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPODOC, WPI, TXTE, TXTG

C DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No

X US 3 567 610 A (KROL et al.) 2 March 1971 (02.03.1971) 1, 6 , 7Claims 1, 12; Description Co/omn 7 Lines 16-24

US 2 916 428 A (STRETTON et al.) 8 December 1959 1-7(08.12.1959)Claims 1, 6; Description Colomn 2 Line 67 - Colomn 3 Line 3

GB 787 930 A (KONINKLIJKE INDUSTRIEELE MAATSCHAPPIJ 1-7VOORHEEN NOURY & VAN DER LANDE) 18 December 1957(18.12.1957)Claims 1, 2; Description Colomn 3 Line 30 - Colomn 4 Line 53

Further documents are listed in the continuation of Box C See patent family annex

* Special categories of cited documents "T" later document published after the international filing date or"A" document defining the general state of the art which is not considered priority date and not in conflict with the application but cited

to be of particular relevance to understand the principle or theory underlying the invention"E" earlier application or patent but published on or after the international "X" document of particular relevance, the claimed invention

filing date cannot be considered novel or cannot be considered to involve"L" document which may throw doubts on priority claim(s) or which is an inventive step when the document is taken alone

cited to establish the publication date of another citation or other "Y" document of particular relevance, the claimed inventionspecial reason (as specified) cannot be considered to involve an inventive step when the

"O" document referring to an oral disclosure, use, exhibition or other document is combined with one or more otheτ suchmeans documents, such combination being obvious to a person

"P" document published prior to the international filing date but later than skilled m the artthe priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

5 August 2009 (05.08.2009) 1 September 2009 (01.09.2009)

Name and mailing address of the ISA/ AT Authorized officer

Austrian Patent Office HUNGER U.

Dresdner Straβe 87, A-1200 Vienna

Facsimile No +43 / 1 / 534 2 4 / 535 Telephone No. +43 / 1 / 534 24 / 363

Form PCMSA/210 (second sheet) (January 2004)

.

PCVlN 2009/000205C (Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

GB 1 297 550 A (M & T CHEMICALS INC.) 22 November 1972 1-7(22.1 1.1972)Claims 1-5

Form PCT/ISA/210 (continuation of second sheet (I)) (January 2004)

Continuation of first sheet

Continuation No. Ii:Observations where certain claims were found unsearchable(Continuation of item 2 of first sheet)

This international search report has not been established in respect of certain claims underArticle 17(2)(a) for the following reasons:

1. With regard to any nucleotide and/or amino acid sequence disclosed in the internationalapplication and necessary to the claimed invention, the international search was carried outon the basis of:

Claims Nos.: 8, 9 because they relate to parts of the international application that do notcomply with the prescribed requirements to such an extent that no meaningful internationalsearch can be carried out, specifically:

Claim 8 presents a product-by-process claim. This certain phrasing is allowed for describingproducts which can be exclusively characterized by their mode of manufacture, which is notthe case here. Claim 9 is a dependent claim of claim 8 and contains no additional technicalfeatures.

Form PCT/ISA/210 (continuation of first sheet (I)) (January 2004)

Information on patent family members PCT/IN 2009/000205

Patent document cited Publication Patent family Publicationin search report date members) date

us A 3567610 US A 3567610 1971-03-02

us A 2916428 us A 2916428 1959-12-08

GB A 787930 DDEE AA ll 11556699007700 1970-04-09FR A 1133139 1957-03-21GB A 787930 1957-12-18NL C 87074C 0000-00-00BE A 541826 0000-00-00

GB A 1297550 CCAA AAll 994455335566 1974-04-16GB A 1297550 1972-11-22ZA A 7008462 1971-10-27IL A 35856 1974-09-10IL A 35855 1975-10-15JP B 48022336B 1973-07-05

Form PCT/ISA/210 (patent family annex) QuIy 1998; reprint January 2004)

WO 2009/122438 Al

Documents

Transcript of WO 2009/122438 Al