Title of Invention

NOVEL ADDUCTS AS BRANCHING AGENTS FOR CONDENSATION POLYMER AND METHOD FOR PRODUCING THE SAME

Abstract Novel adducts are used as branching agent for condensation polymers. The branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol / mono alkyl amine and at least one diol / diamine. A process for the preparation of above adduct is disclosed herein.
Full Text FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
As amended by the Patents (Amendment) Act, 2005
&
The Patents Rules, 2003
As amended by the Patents (Amendment) Rules, 2005
COMPLETE SPECIFICATION
(See section 10 and rule 13)
TITLE OF THE INVENTION
Novel adducts as branching agents for condensation polymer and method
for producing the same.
APPLICANTS
Name : Reliance Industries Limited
Address : Reliance Technology Center, B-4 MIDC Industrial Area, Patalganga 410220,
Dist Raigad, Maharashtra, India
Nationality: Indian company incorporated under the Companies Act 1956
INVENTORS
Name : Nadkarni Vikas Madhusudan
Address: A18 Garden Estate, Off DP Road, Aundh.Pune -411007, Maharashtra, India
Nationality: Indian
Name: Venkatachalam Subbiah
Address : B3, First floor, Flat no 3 , SHIVPARVATI Co-op Housing Society,
Plot no 106-110, Sector 21, Nerul (East)
Navi Mumbai, 400706
Maharashtra India
Nationality: Indian
Name : Honkhambe Pandurang Nagnath
Address: A/P: Bhatambare
Ta. Barshi; Dist. Solapur- 413401
Maharashtra India
Nationality: Indian
Name: Deshpande Amit Avinash Address : 203,Kanuma Apartments Hendrepada Kulgaon Badlapur(W)-421503 Maharashtra, India Nationality: Indian
PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the nature of this invention and the manner in which it is to be performed

FIELD OF THE INVENTION
The present invention relates to novel adducts for use as branching agent for condensation polymers.
The present invention also relates to method for producing the above adducts which are used as branching agent for condensation polymers.
BACKGROUND OF THE INVENTION
Thermoplastic polymers, particularly polyesters are widely used in manufacturing of fibers or filaments or films or container by extrusion, molding (injection or stretch blow). However, the polyester is known for deficiencies in melt rheology. In particular, polyester has typically low melt viscosity, low melt strength and low melt elasticity. With such limitations, the polyester have narrow processing window and specialized equipments are always required for the processing. Generally melt viscosity and melt strength of polyester or any condensation polymer can be improved by introducing branching in the linear chain structure of the polymer and / or increasing molecular weight through chain extension. One approach of introducing branching in polymer is by adding branching agent such as poly-functional carboxylic acids or anhydrides or alcohols directly during the polymerization reaction or melt mixing process. Depending upon the type of branching agent used to modify polyester, the overall effect of the reaction-melt mixing may in fact decrease the molecular weight of the polyester. This will often be the case where the only type of branching agent used is a polyol branching agent. Most widely used branching agents are tri-functional monomers such as 1,2,4 benzene tricarboxylic acid, 1,3,5-Benzenetricarboxylic acid, 1,1,1-Tris(hydroxymethyl)ethane, 1,1,1-Tris(hydroxymethyl)propane and tetra-functional monomer such as pentaerythritol for condensation polymer. Regardless of the type of branching agent used to effectively modify the polymer, it is important that the degree of branching can be controlled during the reaction
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and that the branching occurs uniformly in the polymer. The most simple way in which the agent can be added to the polymer is by direct addition. However, this mode of addition has been found to lead to gel formation through excessive localized chain coupling and non uniform branching within the modified polymer. This also leads to detrimental discolouration. Furthermore, it is not uncommon to use amount of less than 1000 ppm weight percent of the branching agent, relative to the polymer to be modified. At these low levels, it is difficult to provide a uniform distribution of the branching agent in the polymer by direct addition, which leads to non-uniform branching in polymer. The above branching agents, being multifunctional, are active and if used directly in the polymerization reaction, it may be difficult to control the chain length and distribution of branching, which ultimately affects melt viscosity. Thus non-uniform branching makes the polymer product inconsistent in quality including inconsistent polymer rheology, which leads to spinning problem as well as abnormalities in down stream processing.
We have not come across any existing reference of the branching agent, which comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol / mono alkyl amine and at least one diol / diamine as per the invention.
OBJECTS OF THE INVENTION
An object of the invention is to provide novel adducts which comprise at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol / mono alkyl amine and at least one diol / diamine.
Another object of the invention is to provide the above adducts which are used as branching agent for condensation polymers.
Another object of the invention is to provide the above adducts as branching agent for condensation polymers where the final product is cost-effective as there is no occurrence of gelling.
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Another object of the invention is to provide the above adduct as branching agent for condensation polymers where the final product is consistent in quality as the branching occurs uniformly in the polymer chain and controlled chain length.
Another object of the invention is to provide a method for producing the above adducts.
DETAILED DESCRIPTION
According to the invention there is provided novel adducts for use as branching agent for the condensation polymers, said adducts comprise at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol /mono alkyl amine and at least one diol / diamine.
According to the invention there is also provided a process for the preparation of the above adducts which are used as branching agent for condensation polymers, the process comprises
a) condensing at least one tri-functional carboxylic acid or anhydride thereof with at least one mono alkyl alcohol / mono alkyl amine at temperature upto 250° C and under pressure upto 2 Kg/cm2;
b) further reacting with at least one diol / diamine at temperature upto 250° C and under pressure upto 2 Kg/cm2 to form an adduct; and
c) isolating the adduct by evaporation.
The tri-functional carboxylic acid or anhydride thereof is selected from 1,3,5-Benzene-tri-carboxylic acid, 1,2,3-Benzene-tri-carboxylic acid or anhydride thereof, 1,2,4-Benzene-tri-carboxylic acid (Trimelletic acid) or anhydride thereof, 2,3,6-naphthalene tri-carboxylic acid or anhydride thereof, perylene tri-carboxylic acid or anhydride thereof. The mono alkyl alcohol is a long chain alcohol having carbon chain length of C1 to C25 or highly substituted branched aliphatic or aromatic alcohol. Preferably, the long chain mono alkyl alcohol is selected from butanol, hexanol, heptanol, octanol, nonanol or dodecanol. Preferably highly
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substituted branched aliphatic or aromatic alcohol is selected from isobutanol, isooctyl alcohol, isododecyl alcohol, neopentyl alcohol or benzyl alcohol. The mono alkyl amine is highly substituted branched aliphatic amine selected from isopentyl amine, isobutyl amine, isooctyl amine, octyl amine, dodecyl amine or combinations thereof. The diol is selected from monoethylene glycol, 1,3-propane diol, 1,6-hexane diol or butane diol. The diamine is selected from ethylene diamine, 1,3-propane diamine, 1,6-hexane diamine or 1,4-butane diamine. The ratio of Afunctional carboxylic acid or anhydride thereof, mono alkyl alcohol / mono alkyl amine and diol /diamine is 1:0.5:2 to 1:1.5:7. The adduct of the invention is added as a branching agent in the range of 0.1 to 10 % by wt. of the polyester, preferably in the range of 0.4 to 2 % by wt. of the polyester in the polymerization reaction.
According to the invention there is provided use of above adducts as branching agent in condensation polymers. On incorporation of adducts as branching agent in polymer, die swell of the polymer increased with increasing adduct content. This suggests the increased chain entanglement with increased branching and decreased crystallization rate. According to the die swell data, the polyester has uniform branching in the polymer chain and branch length is controlled by controlling chain length of the alkyl group of the branching agent. There is no occurrence of gelling in the polymerization as well as in the product. Thus the final product is cost-effective. The final product is consistent in quality.
Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.
Example 1
1,4- bis(2-hydroxy ethyl) 2-octyl tribenzoate
Trimelletic anhydride (424 g, 2.2 mol) and 1-octanol (287g, 2.2 mol) was heated at 200°C under nitrogen pressure of 25 psi with stirring. The reaction was carried
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out for 4 hours. The reaction mixture was cooled and further depressurized. To this reaction mixture, monoethylene glycol (MEG) (548 g 8.8 mol) was added. The reaction was further carried out at temperature of 220°C under the nitrogen pressure of 25 psi. for 4 hours. The reactor was depressurized and product was drained under hot condition. The product was characterized by NMR and saponification value.
NMR data:
1H-NMR (CDCI3, ppm): 8.5 (d, 1H), 8.2 (dd, 1H), 7.7 (d, 1H), 4.7 (m, 2H), 4.4 (m,
2H), 4.3 (m, 2H), 3.9 (m, 4H), 1.8 (m, 2H), 1.3 (m, 10H), 0.95 (t, 3H). Sap.Value = 410 meq KOH/g
Example 2
1,4- bis(2-hydroxy ethyl) 2-dodecyl tribenzoate
Trimelletic anhydride (412 g, 2.14 mol) and 1-Dodecanol (400g, 2.14 mol) was heated at 200°C under nitrogen pressure of 25 psi with stirring. The reaction was carried out for 4 hours. The reaction mixture was cooled and further depressurized. To this reaction mixture, monoethylene glycol (MEG) (532 g 8.28 mol) was added. The reaction was further carried out at temperature of 220°C under the nitrogen pressure of 25 psi. for 4hours. The reactor was depressurized and the product was drained at hot condition. The product was characterized by NMR and saponification value.
1H-NMR (CDCI3, ppm): 8.47 (d, 1H), 8.23 (dd, 1H), 7.67 (d, 1H), 4.64 (m, 2H),
4.42 (m, 2H), 4.3 (m, 2H), 3.91 (m, 4H), 1.82 (m, 2H), 1.28 (m, 18H), 0.93 (t, 3H). Sap. Value = 360 meq KOH/g
Example 3
Control polyester without adduct
Monoethylene glycol MEG (6 kg) and purified terephthalic acid (PTA) (8 kg) (1:2 molar ratio) was esterified in the presence of Sb203 (2. 8 g) as a catalyst at
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260°C under nitrogen pressure of 1.5 - 1.85 kg / cm2. Polycondensing the esterified mixture at 285°C under reduced pressure of 1-5 mm Hg. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen. The polymer was drained as strands by quenching in a water bath. The strands
are then cut into chips in a pelletizer. The polyester obtained was used as control.
Example 4
Polyester with adduct prepared according to Example 1
Monoethylene glycol MEG (6 kg) and purified terephthalic acid (PTA) (8 kg) (1:2 molar ratio) were esterified in the presence of Sb2O3 (2. 8 g) as a catalyst at 260°C under nitrogen pressure of 1.5 - 1.85 kg / cm2. The branching agent prepared according to the example 1 was added at the end of esterification at 260°C and the resultant reaction mixture was further agitated for 30 minutes. The esterified mixture was polycondensed at 285°C under reduced pressure of 1-5 mm Hg. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen. The polymer was drained as strands by quenching in a water bath. The strands are then cut into chips in a pelletizer. The presence of branching in copolyester was confirmed by GPC, DSC and Rheology. The occurrence of branching is often accompanied by broadening of the molecular weight distribution. Polydispersity data is found to be in the range 3.0 to 3.6 indicating the broadening of molecular weight distribution due the branching (Table 1). Figure 1 illustrates Die swell (referred to as 1) data at various shear rates [referred to as 2 (Sec'1)] measured at barrel temperature of 275 °C using Capillary Rheometer (Die diameter = 1 mm and Die Length = 10 mm) for control
sample (ie without additive), polyester comprising 1% adduct and polyester
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comprising 1.5 % adduct. Die swell of control, polyester comprising 1 % adduct and polyester comprising 1.5 % adduct at various shear rates (Sec-1) are indicated by 3, 4 and 5 respectively. Die swell of the polymer increases with increasing adduct content (Figure 1), this suggests the increased chain entanglement with increased branching. The increased branching should always result in decrease in crystallization rate which is seen (Table 2) from the drop in crystallization temperature as seen from the DSC data.
Table 1: Polydispersity data from GPC analysis:

Resin Polydispersity

Control 2.35
1 mole% adduct 3.08
1.5 mole% adduct 3.64
Table 2: Crystallization temperature data from DSC analysis

Resin Crystallization temperature (°C)

Control 219
1 mole% adduct 208
1.5 mole% adduct 197
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We claim
1. Novel adducts which are used as branching agent for condensation polymer, said branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol / mono alkyl amine and at least one diol / diamine.
2. The adducts which are used as branching agent as claimed in claim 1, wherein the tri-functional carboxylic acid or anhydride thereof is selected from 1,3,5-Benzene-tri-carboxylic acid, 1,2,3-Benzene-tri-carboxylic acid or anhydride thereof, 1,2,4-Benzene-tri-carboxylic acid (Trimelletic acid) or anhydride thereof, 2,3,6-naphthalene tri-carboxylic acid or anhydride thereof, perylene tri-carboxylic acid or anhydride thereof.
3. The adducts which are used as a branching agent as claimed in claim 1, wherein the mono alkyl alcohol is a long chain alcohol having carbon chain length of C1 to C25 selected from butanol, hexanol, heptanol, octanol, nonanol or dodecanol or highly substituted branched aliphatic or aromatic alcohol selected from isobutanol, isooctyl alcohol, isododecyl alcohol, neopentyl alcohol or benzyl alcohol.
4. The adducts which are used as branching agent as claimed in claim 1, wherein the mono alkyl amine is highly substituted branched aliphatic amine selected from isopentyl amine, isobutyl amine, isooctyl amine, octyl amine, dodecyl amine or combinations thereof.
5. The adducts which are used as branching agent as claimed in claim 1, wherein the diol is selected from monoethylene glycol, 1,3-propane diol, 1,6-hexane diol or butane diol.
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6. The adducts which are used as branching agent as claimed in claim 1, wherein the diamine is selected from ethylene diamine, 1,3-propane diamine, 1,6-hexane diamine or 1,4-butane diamine.
7. The adducts which are used as branching agent as claimed in claim 1, wherein the ratio of trifunctional carboxylic acid or anhydride thereof, mono alkyl alcohol / mono alkyl amine and diol / diamine is in the range of 1:0.5: 2 to 1:1.5:7.
8. A process for the preparation of the adducts according to claim 1 which are used as branching agent for the condensation polymer, the process comprises;

a) condensing at least one tri-functional carboxylic acid or anhydride thereof with at least one mono alkyl alcohol / mono alkyl amine at temperature upto 250° C and under pressure upto 2 Kg/cm2;
b) further reacting with at least one diol / diamine at temperature upto 250° C and under pressure upto 2 Kg/cm2 to form an adduct; and
c) isolating the adduct by evaporation.

9. The process as claimed in claim 7, wherein the tri-functional carboxylic acid or anhydride thereof is selected from 1,3,5-Benzene-tri-carboxylic acid, 1,2,3-Benzene-tri-carboxylic acid or anhydride thereof, 1,2,4-Benzene-tri-carboxylic acid (Trimelletic acid) or anhydride thereof, 2,3,6-naphthalene tri-carboxylic acid or anhydride thereof, perylene tricarboxylic acid or anhydride thereof.
10. The process as claimed in claim 7, wherein the mono alkyl alcohol is a long chain alcohol having carbon chain length of C1 to C25 selected from butanol, hexanol, heptanol, octanol, nonanol or dodecanol or highly substituted branched aliphatic or aromatic alcohol selected from isobutanol, isooctyl alcohol, isododecyl alcohol, neopentyl alcohol, benzyl alcohol.
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11. The process as claimed in claim 7, wherein the mono alkyl amine is highly substituted branched aliphatic amine selected from isopentyl amine, isobutyl amine, isooctyl amine, octyl amine, dodecyt amine or combinations thereof.
12. The process as claimed in claim 7, wherein the diol is selected from monoethylene glycol, 1,3-propane diol, 1,6-hexane diol or butane diol.
13. The process as claimed in claim 7, wherein the diamine is selected from from isopentyl amine, isobutyl amine, isooctyl amine or octyl amine, dodecyl amine or combinations thereof.
14.The process as claimed in claim 1, wherein the ratio of Afunctional carboxylic acid or anhydride thereof, mono alkyl alcohol / mono alkyl amine and diol / diamine is in the range of 1: 0.5: 2 to 1:1.5:7.
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Dated this the 23rd day of February 2007


Abstract
Novel adducts are used as branching agent for condensation polymers. The branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol / mono alkyl amine and at least one diol / diamine. A
process for the preparation of above adduct is disclosed herein.
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Documents:

395-MUM-2007-ABSTRACT(1-3-2007).pdf

395-MUM-2007-ABSTRACT(17-3-2011).pdf

395-MUM-2007-ABSTRACT(AMENDED)-(17-3-2011).pdf

395-MUM-2007-ABSTRACT(GRANTED)-(31-5-2011).pdf

395-mum-2007-abstract.doc

395-mum-2007-abstract.pdf

395-MUM-2007-ANNEXURE TO FORM 3(1-4-2011).pdf

395-MUM-2007-ANNEXURE TO FORM 3(24-12-2010).pdf

395-MUM-2007-CANCELLED PAGES(18-3-2011).pdf

395-MUM-2007-CLAIMS(1-3-2007).pdf

395-MUM-2007-CLAIMS(AMENDED)-(17-3-2011).pdf

395-MUM-2007-CLAIMS(AMENDED)-(18-3-2011).pdf

395-MUM-2007-CLAIMS(AMENDED)-(24-12-2010).pdf

395-MUM-2007-CLAIMS(GRANTED)-(31-5-2011).pdf

395-MUM-2007-CLAIMS(MARKED COPY)-(24-12-2010).pdf

395-MUM-2007-CLAIMS(MARKED COPY)-(24-12-2011).pdf

395-mum-2007-claims.doc

395-mum-2007-claims.pdf

395-mum-2007-correspondance-received.pdf

395-MUM-2007-CORRESPONDENCE(1-4-2011).pdf

395-MUM-2007-CORRESPONDENCE(11-2-2011).pdf

395-MUM-2007-CORRESPONDENCE(24-12-2010).pdf

395-MUM-2007-CORRESPONDENCE(IPO)-(31-5-2011).pdf

395-mum-2007-correspondence-received.pdf

395-mum-2007-description (complete).pdf

395-MUM-2007-DESCRIPTION(COMPLETE)-(1-3-2007).pdf

395-MUM-2007-DESCRIPTION(GRANTED)-(31-5-2011).pdf

395-MUM-2007-DRAWING(1-3-2007).pdf

395-MUM-2007-DRAWING(GRANTED)-(31-5-2011).pdf

395-mum-2007-drawings.pdf

395-mum-2007-form 13(17-3-2011).pdf

395-mum-2007-form 13(24-12-2010).pdf

395-mum-2007-form 18(13-8-2007).pdf

395-MUM-2007-FORM 2(COMPLETE)-(1-3-2007).pdf

395-MUM-2007-FORM 2(GRANTED)-(31-5-2011).pdf

395-MUM-2007-FORM 2(TITLE PAGE)-(17-3-2011).pdf

395-MUM-2007-FORM 2(TITLE PAGE)-(COMPLETE)-(1-3-2007).pdf

395-MUM-2007-FORM 2(TITLE PAGE)-(GRANTED)-(31-5-2011).pdf

395-MUM-2007-FORM 26(17-3-2011).pdf

395-MUM-2007-FORM 26(24-12-2010).pdf

395-MUM-2007-FORM 3(1-3-2007).pdf

395-MUM-2007-FORM PCT-ISA-210(24-12-2010).pdf

395-mum-2007-form-1.pdf

395-mum-2007-form-2.doc

395-mum-2007-form-2.pdf

395-mum-2007-form-3.pdf

395-MUM-2007-MARKED COPY(17-3-2011).pdf

395-MUM-2007-PETITION UNDER RULE 137(1-4-2011).pdf

395-MUM-2007-REPLY TO EXAMINATION REPORT(24-12-2010).pdf

395-MUM-2007-REPLY TO FIRST EXAMINATION REPORT(24-12-2010).pdf

395-MUM-2007-REPLY TO HEARING(17-3-2011).pdf

395-MUM-2007-REPLY TO HEARING(18-3-2011).pdf

395-MUM-2007-SPECIFICATION(AMENDED)-(17-3-2011).pdf

395-MUM-2007-WO INTERNATIONAL PUBLICATION REPORT A3(24-12-2010).pdf

395-MUM-2007-WO INTERNATIONAL PUBLICATION REPORT(1-3-2007).pdf


Patent Number 247889
Indian Patent Application Number 395/MUM/2007
PG Journal Number 22/2011
Publication Date 03-Jun-2011
Grant Date 31-May-2011
Date of Filing 01-Mar-2007
Name of Patentee RELIANCE INDUSTRIES LTD.
Applicant Address RELIANCE TECHNOLOGY CENTRE, B-4 MIDC INDUSTRIAL AREA, PATALGANGA-410220, DIST RAIGAD,
Inventors:
# Inventor's Name Inventor's Address
1 NADKARNI VIKAS MADHUSUDAN A18 Garden Estate, Off D P Road, Anudh, Pune-411007
2 VENKATACHALAM SUBBIAH B3,First Floor, Flat no 3, SHIVPARVATI Co-op Housing Society, Plot no 106-110, Sector 21, Nerul (East), Navi Mumbai, 400706
3 HONKHAMBE PANDURANG NAGNATH A/P Bhatambare, Ta: Barshi, Dist Solapur-413401
4 DESHPANDE AMIT AVINASH 203, Kanuma Apartments, Hendrepada Kulgaon, Badlapur (W)-421503
PCT International Classification Number C08L67/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA