NL1004951C2 - Antistatic peroxide composition. - Google Patents

Description

The invention relates to a new peroxide composition, to a process for the preparation and to the use thereof.

Static electricity is a major problem in the preparation, storage, transportation and use of a peroxide composition. Discharge of this static electricity creates the risk of electric shock and sparks. The electric shocks are bothersome and sometimes even dangerous to humans. If a flammable atmosphere is present, the sparks may cause a fire and / or explosion, for example due to the volatility of the peroxide used.

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Generally, the danger of static electricity build-up arises when the electrical conductivity of a peroxide composition is low. For example, di-tert-amyl peroxide (Trigonox® 201) has an electrical conductivity of less than 20 pS / m. A particularly dangerous situation can arise when both the electrical conductivity and the flash point of a peroxide composition are low. This is the case, for example, with di-tert-butyl peroxide (Trigonox® B), which has an electrical conductivity of 0.4 pS / m and a flash point of 6 ° C. The flash point of di-tert-amyl peroxide, on the other hand, is 29 ° C. In general, it can be said that when a peroxide composition has an electrical conductivity of less than 50 pS / m and a flash point of less than 40 ° C, there is a dangerous situation as described above. Also, the use of dilutions in non-conductive solvents, such as hydrocarbons, can lead to a low (re) electrical conductivity of a peroxide composition. A solution has now been found to the problem of a peroxide composition with a low electrical conductivity.

1004951 2

The peroxide composition of the present invention is characterized in that the composition comprises a dialkyl peroxide and an effective amount of an antistatic.

A great advantage of the anti-static peroxide composition according to the invention is that there is no charge build-up during transport in pipes, stirring and other process operations and that it can be safely packed in the usual non-conductive containers for transport and storage. Furthermore, the conductivity of the peroxide composition during the required storage period is sufficiently high and no interfering influences occur in its application, because only a small amount of antistatic need be added to make the composition sufficiently electrically conductive.

The dialkyl peroxide composition according to the invention preferably comprises a di-tert-alkyl peroxide. Most preferred is a composition comprising di-tert-butyl peroxide (Trigonox® B) or di-tert-amyl peroxide (Trigonox® 201). Preferably, the peroxide composition contains 5-99.9 percent of this peroxide.

Antistatic agents in the present description include, in addition to simple substances, also polymers, as well as compositions and mixtures of these substances. An effective amount of an antistatic is understood to mean an amount that results in a peroxide composition with an electrical conductivity greater than 50 pS / m. Preferably, the peroxide composition of the invention comprises less than 1000 ppm of an antistatic based on the weight of peroxide in the composition. The electrical conductivity is measured using an Eltex Tera Ohm meter and a conductivity cell for liquids as described in the experimental section. Most preferred is a peroxide composition containing less than 400 ppm of an antistatic, which amount results in an electrical conductivity greater than 1000 1004951 3 pS / m. The peroxide composition of the present invention usually contains 0.5-50 ppm of an antistatic.

Good electrical conductivity of the peroxide composition of the present invention is obtained if the antistatic comprises an organic acid or a salt thereof, a salt of an inorganic acid, or a mixture of these substances.

Suitable organic acids are polymeric compounds containing one or more sulfuric, sulfonic, carboxylic, phosphoric or phosphonic acid groups. Other suitable organic acids are sulfuric acids, sulfonic acids, carboxylic acids, phosphoric acids or phosphonic acids or substituted by one or more C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or C7-C30 alkaryl radicals. hydrates thereof, which are branched or unbranched radicals and which may or may not contain one or more hydroxy, alkoxy, carboxy, amide or ester groups.

Suitable organic acid salts are one or more alkyl, C 2 -C 20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or C7-C30 alkaryl radicals substituted in the anion or cation, ammonium and quaternary ammonium sulfates, sulfonates. 20, carboxylates, phosphates or phosphonates or hydrates thereof, which radicals are branched or unbranched and may or may not contain one or more hydroxy, alkoxy, carboxy, amide or ester groups. Metal ion salts of the said anions are also suitable. Suitable metal ions are, for example, alkali metal, alkaline earth metal or transition metal ions.

25

Suitable salts of inorganic acids are substituted by one or more C 1 -C 4 alkyl, C 2 -C 20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or C7-C30 alkaryl radicals, which radicals branched or are unbranched and may or may not contain one or more hydroxy, alkoxy, carboxy, amide or ester groups. Also suitable are the corresponding sulfates or phosphates.

1004951 4

Those skilled in the art will have no difficulty, for example, depending on the peroxide to be used and the desired application, to choose a suitable antistatic from these acids and salts. Preferably, the antistatic comprises one or more of the following: para-toluenesulfonic acid monohydrate, dodecyl-5-benzenesulfonic acid, ethoxylated and phosphated nonylphenol, copper or chromium dialkyyl salicylate, sodium (sec-C13-C17-alkyl) sulfonate, sodium or calcium dialkyl sulfosuccinate, di (hydrogenated talc) -dimethylammonium methosulfate, di-decyldimethylammonium chloride, a polymeric compound containing sulfonic acid, sulfonate and sulfone groups, or a polymeric compound containing carboxylic acid and amide groups. A suitable antistatic is, for example, ASA-3.

The peroxide composition of the invention may optionally comprise a solvent, diluent or oil or a mixture thereof. Liquids known to those skilled in the art are alcohols, such as, for example, n-butyl alcohol, tert-butyl alcohol, tert-amyl alcohol, n-propyl alcohol and isopropyl alcohol; hydrocarbons, such as, for example, isododecane; esters of dicarboxylic acids, such as, for example, dibutyl phthalate and mineral oils. Preferably, less than 0.5 weight percent of the liquid or mixture of liquids, based on the weight of peroxide, will be present in the peroxide composition. It should be noted here that some liquids may not be suitable for use in the peroxide composition of the invention; for example, because the liquid presents problems in the application of the peroxide composition. Most preferred is tert-butyl alcohol and tert-amyl alcohol.

In the method according to the invention an effective amount of an antistatic agent, as defined above, is added to a dialkyl peroxide or a formulation thereof, such as for instance a solution or an emulsion. It is preferable to first dissolve the antistatic in a suitable agent, as mentioned above, before adding the antistatic to the peroxide or a formulation thereof. It is important herein to ensure that the antistatic is in solution at the temperature at which the peroxide composition is stored, transported and handled.

The peroxide composition of the present invention can be a liquid, whether or not formulated as a solution or emulsion, or phlegmatized. Suitable phlegmatizers are known to the person skilled in the art, such as, for example, silicone oil, "white oils" and high-boiling hydrocarbons, such as, for example, isododecane.

Furthermore, the peroxide composition may include adjuvants known to those skilled in the art such as emulsifiers, stabilizers, anti-ozonants, antioxidants, anti-degradants, UV stabilizers, fungicides, coupling agents, lubricants, blowing agents, release agents and nucleating agents.

The anti-static peroxide composition of the present invention can be used to initiate radical (co) polymerizations, cure and crosslink rubber and thermoset formulations, and perform (co) polymer modification processes, chemical reactions and other processes involving peroxides .

The invention is further illustrated by the following non-limiting examples.

EXPERIMENTAL SECTION

25 Materials

Tx B Trigonox® B, di-tert-butyl peroxide, ex Akzo Nobel DTAP Trigonox® 201, di-tert-amyl peroxide, ex Akzo Nobel

Aerosol OT-100 Sodium di (2-ethylhexyl) sulfosuccinate, 100%, ex Cytec 30 Armac C Cocoamine acetate, ex Akzo Nobel 1004951 6

ArmostateOO Triethanolamine n-dodecylbenzene sulfonate, 53% in water, ex Akzo Nobel

Arquad2.10 Didecyldimethylammonium Chloride, 83%, ex Akzo

Nobel 5 Arquad 2T-70 Di-tallow dimethylammonium chloride, 70% in 2-propanol, ex Akzo Nobel

Arquad M2HT-90MS Di- (hydrogenated ta! K) -dimethylammonium methosulfate, ex Akzo Nobel ASA-3 A mixture of 20% chromium (III) di (C16-C18alkyl) - 10 salicylate, 10% calcium bis (diisodecyl sulfosuccinate) , 45% 2-methyl-5-vinylpyridine (C16-C18-alkyl) methacrylate copolymer, 25% meta-xylene, ex Shell BSA Benzenesulfonic acid, 90%, ex Acros

CuDIPS Cu (ll) 3,5-diisopropylsalicylate hydrate, ex Aldrich 15 DBSA Dodecylbenzenesulfonic acid, 97%, ex Janssen

Gafac RM710 Anionic Soap, 100%, ex GAF Chemical Corp.

Marlon PS65 Sodium (sec-C13-C17-alkyl) sulfonate, 65%, ex Hüls

Marlon-NH4 Ammonium salt of Marlon PS65 MSA Methylsulfonic acid,> 99%, ex Aldrich 20 PAPSA Poly (2-acrylamido-2-methyl-1-propanesulfonic acid), dried, ex Aldrich ΡΕΜΑ Copolymer of methyl vinyl ether and maleic anhydride, Mw 311000, ex Aldrich

ServonXCA850 Calcium bis (di-isodecyl sulfosuccinate), 50% in xylene, 25 ex Hüls

Servoxyl VPI 55 Phosphoric acid, butyl ester, sodium salt, 50-100%, ex Hüls

Servoxyl VPIZ100 1-butanol, phosphated, 50-100%, ex Hüls

Servoxyl VPNZ 5/100 (or NPEP) Nonylphenol, ethoxylated, phosphated, ex Hüls 30 Stadis 450 A mixture of, inter alia, DBSA, a quaternary ammonium salt and a polymeric compound containing 1004951 7 sulfonic acid, sulfonate and sulfone groups, in toluene isopropyl alcohol, ex Du Pont (Octel) TBAI Tert-butyl alcohol, ex Baker TBAm Tributylamine, ex Baker 5 TEP Triethyphosphate, ex Baker

TSA Toluene-4-sulfonic acid.H20,> 99%, ex BDH AnalaR

TIM Toluene Isopropyl Alcohol-Methanol Mixture ZFA Zirconium (IV) Trifluoroacetylacetonate, 97%, ex Aldrich 10 Electrical Conductivity

The electrical conductivity, expressed in pS / m, was measured using an Eltex Tera Ohm Meter (type 6206) and a stainless steel immersion cell, consisting of two concentric cylindrical electrodes, with a cell constant of K = 1.65 1 / m . Conductivity was measured 1 day after sample 15 preparation. The measurements were performed at room temperature (19-23 ° C). The resistance was read 1 minute after immersion of the cell.

Table I shows the results for di-tert-butyl peroxide (Trigonox® B, Tx B) 20 of Comparative Examples A-D and Examples 1-16. The amount of antistatic is expressed in mg per kg (ppm) Tx B.

1004951 8

Table I

Conductivity of Tx Β with antistatic

Antistatic Concentration Conductivity ___ (mg / kg) __ (pS / m) A None 0 0.4 B TSA 51 3 C TBAI 1500 2.5 D Arquad M2HT-90MS, 13% in TBAI 250 3.5 1 DBSA 59 60 2 Gafac RM710, 30 min. Ultrasonic 110 70 3 Gafac RM710, 10% in TBAI 1000 120 4 Armostat 800 1000 750 5 Armac C 50 50 6 Aerosol OT-100 50 165 7 Aerosol OT-100 260 525 8 Marlon PS65, 10 min. ultrasonic 99 750 9 Marlon PS65, 10 min. ultrasonic 145 2750 10 Marlon ~ NH4 150 2000 11 CuDIPS 251 1100 12 ZFA 253 600 13 Stadis 450 5 750 14 Servoxyl VPNZ 5/100 50 1050 15 Servoxyl VPNZ 5/100 249 7000 16 ASA -3 4.7 2360 17 PAPSA 49 61 18 Servon XCA 850 255 500 1004 951 9

Marlon-NH4 was prepared by passing a solution of Marlon PS65 in water over a strong acid ion exchanger and neutralizing the eluate with 1% NH4OH to pH 6. The resulting salt was obtained in vacuo from the water.

5

Table I shows that with Aerosol OT-100, Marlon PS65, CuDIPS, ZFA, Stadis 450, Servoxyl VPNZ 5/100, ASA-3 and Servon XCA 850 in particular, a good improvement in the electrical conductivity of Tx B can be achieved.

10 Stability

Table II gives the results of a stability study of Tx B compositions with 247 ppm Marlon PS65.

Table II

15 Conductivity of Tx B with Marlon PS65 = -...- 1-11 - - i = aaaaaaaaiaMg "1.1 1

Storage time Conductivity (pS / m) after storage at: (weeks)

^ fc 4ÖX

1 0.15 6600 0.6 4850 8550 1 3950 7500 2.8 3300 4700 5.15 3000 5800 14.7 2750 3235

Table II shows that the conductivity of Tx B with 247 ppm Marlon PS65 decreases slowly during storage, but remains sufficiently high to prevent static charging of the peroxide in well-grounded systems.

1004951 10

Table III shows the results of Comparative Examples E and F and Examples 19-29. First, a 15-20 weight percent solution of an acid with an amine or quaternary amine was made which was then added to Tx B. The concentration represents the amount of the antistatic-5 solution in mg per kg (ppm) Tx B. The molar ratio indicates the ratio between the acid and the Arquad or the amine.

Table III

Conductivity of Tx B with Antistatic 10

Antistat. Conc. Acid Arquad / amine Solvent. Molverh. Guide bra (mg / kg) (pS / m) E Astat2 1026 DBSA Arq. 2T-70 TIM 1: 0.62 15 F Astat 3 999 DBSA TBAm TIM 1: 0.52 15 19 Astat5 966 DBSA Arq. 2.10 TIM 1: 0.43 65 20 Astat6 500 TSA Arq. M2HT-90MS TBAI 1: 0.50 5050 21 Astat6 250 TSA Arq .M2HT-90MS TBAI 1: 0.50 1550 22 Astat6 50 TSA Arq.M2HT-90MS TBAI 1: 0.50 75 23 Astat7 1008 MSA Arq.M2HT-90MS TBAI 1: 0.504 3400 24 Astat9 1008 TSA TBAm TBAI 1: 1.03 85 25 Astat18 250 BSA Arq.M2HT-90MS TBA / IPA 1: 0.50 310 26 Astat 20 77 1) 1: 1.53 440 27 Astat 21 210 2) 1: 0.50 85 28 Astat 23 250 3) 1: 0.80 780 29 Astat 46 294 4) 1 : 2 190 1) Astat 20 consists of a mixture of CuDIPS and Aerosol OT-100 in a molar ratio of 1: 1.53.

1004951 11 2) Astat 21 consists of a mixture of a solution in TBAI of Arq.M2HT-90MS and Aerosol OT-100 in the molar ratio of 1: 0.50.

3) Astat 23 consists of a mixture of a solution in TBAI of Arq.M2HT-90MS and Servoxyl VPNZ 5/100 in a molar ratio of 1: 0.80.

5 4) Astat 46 is the reaction product of ΡΕΜΑ and dodecylamine, 17.6% in xylene in a 1: 2 molar ratio.

It can be deduced from Table III that the mixture Astat6, a solution of Arq.M2HT-90MS and TSA in TBAI, gives a good improvement of the electrical conductivity of Tx B.

The application and safety study on Tx B was performed with a reference sample Tx B and a sample to which 1000 mg of antistatic agent per kg Tx B was added. The antistatic consists of: 69 mg of 15 para-toluenesulfonic acid monohydrate, 122 mg of Arquad M2HT-90MS and 810 mg of tert-butyl alcohol as a solvent.

Application of Tx B in the preparation of polvacrvate

The influence of a Tx B antistatic on the acrylic properties was determined by a model reaction performed with a monomer mixture in a solvent. The monomer mixture consists of 40% butyl acrylate, 20% styrene, 28% hydroxyethyl methacrylate, 10% methyl methacrylate and 2% methacrylic acid. The reaction was carried out in Solvesso 100 at 165 ° C, the initiator was dosed over 4 hours.

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The solid content was determined as a percentage of non-volatile material after 30 minutes at 150 ° C. Molecular weight was determined by HPLC analysis, polystyrene standard samples used as references. The color was measured in a 'Lovibond' APHA meter. The results are shown in Table 30 IV.

1004951 12

Table IV

Results of Tx B in the “high solids” air preparation

| System Solids Mw Mn Color APHA

(%) with antistatic 72.6 4200 2000 30 reference 72.9 4100 2000 30 5 From the measurement results of the model system it can be concluded that the antistatic has no influence on the polymer properties; molecular weight, solids percentage colors are comparable.

Safety 10 The product safety properties of Tx B with antistatic were tested according to the UN flowchart. The methods are described in 'Recommendations on Transport of Dangerous Goods', Second edition. The results of the UN tests with conductive Tx B are equal to the results of a reference sample.

The product is; - not sensitive to detonation, not sensitive to deflagration, the pressure effect on heating under defined conditions is "Low" (tests with 50 g have not been carried out), the explosive force measured in the HPA (High 20 Pressure Autoclave) is "Not Low" ,

the SADT is greater than or equal to 90 ° C

Additional tests: - the product is not impact sensitive and not sensitive to friction, 1004951 13 the electrical conductivity is greater than 3000 pS / m, the reference sample has a conductivity of 0.4 pS / m.

Table V gives the results for di-tert-amyl peroxide (DTAP, Trigonox® 201) in comparative example G and examples 30-33. The composition of Astat 6 is shown in Table III.

Table V

10 Conductivity of DTAP with antistatic

Antistatic Concentration Conductivity (mg / kg) (pS / m) G None 0 20 30 Marlon PS65 257 900 31 Stadis 450 57 10000 32 ServoxylVNPZ 5/100 358 4000 33 Astat 6 698 400

Table V shows that Marlon PS65, Stadis 450 and Servoxyl VPNZ 5/100 significantly increase the electrical conductivity of DTAP.

1004951 14

Table VI gives the results of a stability study after storage at room temperature of some anti-static DTAP formulations.

Table VI

5 Stability of DTAP compositions

Antistatic Conductivity (pS / m) after 1 day after 5 weeks

None 20 15

Marlon PS65, 257ppm 900 800

Astat 6,698 ppm 400 800

Stadis 450, 57 ppm 10000 5300

Servoxyl VPNZ 5/100, 358 ppm 4000 85

Table VI shows that Marlon PS65, Astat 6 and Stadis 450 are stable and provide a persistently good conductive DTAP composition.

10

The foregoing examples are illustrative of the present invention only. The scope of the invention is determined on the basis of the following claims.

1004951

Claims (11)

Peroxide composition, characterized in that the composition comprises a dialkyl peroxide and an effective amount of an antistatic. 5 Peroxide composition according to claim 1, characterized in that the dialkyl peroxide is di-tert-butyl peroxide or di-tert-amyl peroxide. 3. Peroxide composition according to claim 1 or 2, characterized in that the antistatic comprises an organic acid, a salt thereof, a salt of an inorganic acid, or a mixture of these substances. 4. Peroxide composition according to claim 3, characterized in that the organic acid is a polymeric compound containing one or more sulfuric, sulfonic, carboxylic, phosphoric or phosphonic acid groups. 5. Peroxide composition according to claim 3, characterized in that the organic acid is one which contains one or more alkyl, C2-C20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or C7-C30 alkaryl radicals substituted sulfuric acid, sulfonic acid, carboxylic acid, phosphoric acid or phosphonic acid or a hydrate thereof, which is radically branched or unbranched and which may or may not contain one or more hydroxy, alkoxy, carboxy, amide or ester groups. 6. Peroxide composition according to claim 3, characterized in that the salt of an organic acid is one which contains one or more C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or C7-C30 alkaryl radicals, ammonium or quaternary ammonium sulfate, sulfonate, sulfonate, carboxylate, phosphate, or phosphonate substituted in the anion or cation, which is radically branched or unbranched and may or may not contain one or more hydroxy, alkoxy, 30 contains carboxy, amide or ester groups. 1004951 The peroxide composition according to claim 3, characterized in that the salt of an inorganic acid is one by one or more C1-C20 alkyl, C2-C20 alkenyl, C6-C18 aryl, C7-C30 aralkyl or Ct- C 1-4 alkaryl radicals are substituted ammonium or quaternary ammonium halide, sulfate or phosphate which is radically branched or unbranched and which may or may not contain one or more hydroxy, alkoxy, carboxy, amide or ester groups. Peroxide composition according to any one of the preceding claims, characterized in that the composition contains less than 1000 ppm of an antistatic, based on the weight of peroxide. Peroxide composition according to any one of the preceding claims, characterized in that the composition also comprises a solvent, diluent or oil, or a mixture thereof. 15 Process for the preparation of a peroxide composition, characterized in that an effective amount of an antistatic as defined in any one of the preceding claims is added to a dialkyl peroxide, or a formulation thereof. 20 11. Use of an anti-static peroxide composition according to any one of the preceding claims 1-9, for initiating radical (co) polymerizations, curing and crosslinking of rubbers and thermosetting formulations and carrying out (co) polymer modification processes, chemical reactions and other processes involving peroxides. 1004951 COOPERATION TREATY (PCD REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE OF IDENTIFICATION OF THE NATIONAL APPLICATION Characteristic of the applicant or of the authorized representative ACD 2561 PDNL NtdarlandM application no. Submission date 1004951 Priority date APPLICATED on the Applicant (name of the applicant) International Type Examination Issued by the International Research Authority (ISA) to the request for an International Type Examination No SN 28933 EN I. CLASSIFICATION OF THE SUBJECT (When using different classifications. Provide all classification symbols) According to the International Classification (IPC Int. Cl. 6: C 09 K 3/16, C 07 C 409/00, C 08 F 4/32 II AREAS OF TECHNIQUE EXAMINED Minimum documentation examined Classification system Classification symbols Int. Cl. 6 C 09 K, C 07 C, C 08 F Examined documentation other than minimum documentation to the extent that such documents Ml. [| NO RESEARCH POSSIBLE FOR CERTAIN CONCLUSIONS (Comments on Supplementary Sheet) x - ^ IV- I [LACK OF UNIT OF INVENTION (Comments on Supplementary Sheet) Form PCT / ISA / 20K ») 07.1979