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WO1997011048A1 - Diester and the use thereof as hydrophilising agent in pvc - Google Patents

Diester and the use thereof as hydrophilising agent in pvc Download PDF

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Publication number
WO1997011048A1
WO1997011048A1 PCT/SE1996/001053 SE9601053W WO9711048A1 WO 1997011048 A1 WO1997011048 A1 WO 1997011048A1 SE 9601053 W SE9601053 W SE 9601053W WO 9711048 A1 WO9711048 A1 WO 9711048A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
pvc
diester
group
set forth
Prior art date
Application number
PCT/SE1996/001053
Other languages
English (en)
French (fr)
Inventor
Bengt Nilsson
Steinar Pedersen
Original Assignee
Akzo Nobel N.V.
Norsk Hydro A.S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V., Norsk Hydro A.S filed Critical Akzo Nobel N.V.
Priority to AU71016/96A priority Critical patent/AU7101696A/en
Publication of WO1997011048A1 publication Critical patent/WO1997011048A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • This invention relates to a diester which is compatible with PVC and imparts a hydrophilic quality to it.
  • the diester is distinguished by the fact that its ester groups have different HLB values.
  • Polyvinyl chloride is a polymeric material which is widely used in several major fields of application. Among other things, PVC to which suitable plasticisers have been added is used as outer layer in flooring materials and wallpaper. Even though PVC is an excellent material, there is a need for producing hydrophilic PVC compositions which, for instance, are suitable for use as outer layers in flooring materials, building boards and wallpaper, thereby facilitating the cleaning thereof and reducing the risk of soiling.
  • US-A-3,935,368 teaches the coating of a PVC flooring material with an outer layer of a hydrophilic acrylic polymer in order to facilitate cleaning and prevent soiling.
  • BE- A3-l,004,521 and JP 63 301 234 disclose similar technical solutions, according to which PVC is coated with hydrophilic polymeric materials.
  • hydrophilic PVC is produced by polymerising vinyl chloride with alkyl acrylate and copolymerisable monomers containing hydrophilic groups.
  • JP 49 039 641 polyvinyl alcohol is admixed with PVC in order to give the latter a more hydrophilic nature.
  • the methods described above change the physical and chemical properties of the PVC material markedly, thus obstructing the use of the PVC material in conventional fields of application.
  • the method of coating the PVC material with an outer layer having a completely different chemical structure entails a number of new and, of course, undesirable problems.
  • SUBSTITUTE SHEET which recalls that of plasticisers commonly used in combination with PVC, such as dioctyl phthalate.
  • the new diester alters the hydrophilicity of the PVC material and simultaneously has a plasticising effect. Accordingly, the diester may wholly or partly replace the plasticisers previously used.
  • the diester according to the invention is characterised in that it has the general formula
  • R is a divalent hydrocarbon group having 2-12 carbon atoms, preferably 2-6 carbon atoms
  • Rl is a hydrophobic group having 6-28 carbon atoms, preferably 8-22 carbon atoms, and 0-3 oxygen atoms, preferably 0-2 oxygen atoms, the group R], having an HLB value ranging from -2.6 to 4.2, preferably from -1.7 to 3.3, as determined according to Davies
  • R 2 is a hydrophilic group having 5-45 carbon atoms, preferably 9-30 carbon atoms, and 2-20 oxygen atoms, preferably 4-12 oxygen atoms, the group R 2 having an HLB value ranging from 6.8 to 13.1, preferably from 7.8 to 10.5, as determined according to Davies.
  • the groups R x and R 2 contain only carbon, hydrogen and oxygen, oxygen being a requisite part of R 2 only.
  • the groups R x and R 2 have a hydrocarbon group free from oxygen in end position.
  • the oxygen atoms form ether groups, but they may also be included in one or more hydroxyl groups.
  • the diester according to the invention acts as a conventional PVC plasticiser and, when used in a suitable amount, gives the PVC material essentially the same softness, hardness and plasticising temperature as conventional plasticisers, but also a higher degree of hydrophilicity.
  • PVC sheets containing this diester are much easier to clean and much less liable to get soiled than conventional PVC sheets containing conventional plasticisers, such as dioctyl phthalate. Accordingly, the PVC sheets according to the invention are suited for use as outer layers in building boards, such as kitchen worktops or kitchen doors, floors and wallpaper.
  • a PVC mixture containing the diester may, in addition, be used in existing plants for producing suitable PVC sheets, while requiring but a minimum of changes in the production process.
  • diesters are those compounds of formula (I) which are encompassed by the formula O ⁇ CO(Z 1 ) zl (A) a (Z 2 ) 22 R 3 R (II) CO(Z 3 ) z3 (B) b (Z 4 ) z4 R 4 O
  • R has the designation indicated above, A and B de ⁇ signate, independently of each other, an alkyleneoxy group having 2-4 carbon atoms, preferably 2 carbon atoms, a is a number in the range of 0-3, preferably 0-2, b is a number in the range of 2-20, preferably 4-12
  • R 3 is a hydrocarbon group having 6-22 carbon atoms, preferably 8-18 carbon atoms
  • R 4 is a hydroxyl group or hydrocarbon group having 1-6 carbon atoms, preferably 1-4 carbon atoms
  • Z 1# Z 2 , Z 3 and Z 4 designate the group - CH 2 CH(OH) CH 2 -, and z 1 , z 2 , z
  • the group R 3 may be a straight or branched, saturated or unsaturated aliphatic group, such as 2-ethylhexyl, decyl, dodecyl, oleyl, coconut alkyl, tallow alkyl and rape alkyl, but also an aromatic group, such as butyl phenyl, dioctyl phenyl, 2-ethylhexyl phenyl, n-octyl phenyl or nonyl phenyl.
  • R 3 is an aliphatic group having more than 16 carbon atoms, it may advantageously contain one or more double bonds.
  • R 4 is an alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. Methyl groups are preferred.
  • z l t z 2 , z 3 and z 4 usually designate 0.
  • the diester according to the invention is suitably produced by causing a dicarboxylic acid of formula R(COOH) 2/ wherein R has the designation indicated above, or an anhydride thereof, to react with a hydroxyl compound of formula R ⁇ H, wherein R x has the designation indicated above, in approximately equimolar amounts at a temperature of 100-140°C.
  • the molar ratio of the dicarboxylic acid to the alcohol ranges from 1.0:1 to 1:1.2.
  • Suitable dicarboxylic acids are, for instance, phthalic acid, adipic acid, azelaic acid and trimellitic acid.
  • an organic solvent for instance toluene
  • a hydroxyl compound of formula R 2 OH wherein R 2 has the designation indicated above
  • an esterification catalyst for instance tetra- isopropyl titanium.
  • This reaction mixture is then reacted at 200-240°C.
  • the esterification of the second carboxyl group requires more powerful reaction conditions than does the esterification of the first carboxyl group.
  • the reac ⁇ tion is carried out under vacuum, such that the solvent and the water are evaporated, the water being separated from the solvent, which is recycled.
  • the reaction process is monitored by checking the acid number, and the reaction is suitably interrupted when the acid number is ⁇ 0.02 millimole equivalents per gramme of reaction mixture. Thereafter, the reaction mixture is suitably processed by treating the hot reaction solution with sodium bicarbonate, whereupon the solution is cooled and small amounts of water are added. Volatile components, such as water and solvents, are removed by vacuum distillation, and the remaining product is filtered.
  • the diester can be produced by causing a dicarboxylic acid of formula R(COOH) 2 , wherein R has the designation indicated above, or an anhydride thereof, to react with a mixture of hydroxyl compounds of formulae R ⁇ H and R 2 OH, wherein R x and R 2 have the designations indicated above, in approximately equimolar amounts in relation to the dicarboxylic acid or the anhydride.
  • the preferred molar ratios indicated above are applicable also to this case.
  • the reaction is carried out in a first stage at a temperature of 100-140°C, suitably in the absence of a catalyst, and in a second stage at a temperature of 200-240°C in the presence of an esterification catalyst. Processing may then be performed in the same manner as when the hydroxyl compounds are added separately.
  • PVC material for instance PVC sheets
  • a dispersion of PVC powder in one or, which is usually the case, more plasticisers.
  • C 4 -C 12 -hydrocarbon esters such as phthalates, adipates, azelates, sebacates, trimellitates and phosphates, are among the plasticisers most commonly used.
  • Typical examples are dibutyl phthalate, butyl benzyl phthalate, tricresyl phthalate, dioctyl phthalate, dioctyl sebacate, diisodecyl adipate, dioctyl azelate, ditridecyl phthalate, trioctyltrimellitate and triaryl phosphate.
  • Chlorine-containing paraffins and polymeric plasticisers, such as polyesters and polyadipates, may also be used as plasticisers.
  • the total plasticiser content, including the diester, of a PVC material according to the invention usually is 25-65%, preferably 30-60%, based on the weight of PVC.
  • the diester usually makes up 10-100% by weight, preferably 30-60% by weight, of the total amount of plasticiser and constitutes 2.5-65% by weight, preferably 7.5- 39% by weight, based on the amount of PVC.
  • the PVC material may contain a number of other additives, such as heat stabilisers, colourants and pigments, fillers, ultraviolet absorbants, antistatic agents and viscosity-reducing agents.
  • a surface coating of PVC material according to the invention is produced in conventional manner.
  • a PVC plastisol or a PVC dry mixture containing a diester according to the invention and the other additives are produced in conventional manner.
  • the hydrophilicity of the PVC material can be adjusted by the amount of diester added and the choice of diesters containing suitable hydrophobic groups (R and RJ and suitable hydrophilic groups (R 2 ) .
  • the surface of the PVC material has such a hydrophilicity that the contact angle between the surface and a water drop applied thereto is less than 40° at a temperature of 20° and after 4 min.
  • Phthalic acid anhydride and an alcohol of formula C 13 H 27 ⁇ H were mixed in a molar ratio of 1:1 and heated to a temperature of about 120°C.
  • 30 ml of toluene, 1.05 mole of an ethoxylate of formula CH 3 (OC 2 H 4 ) 10 OH and 0.01 mole of tetraisopropyl titanium were batched per mole of phthalic acid anhydride.
  • the mixture was heated to a temperature of 220°C, at which the reaction was allowed to continue for 6 h under vacuum, such that reaction water could be removed.
  • This product will in the following be referred to as compound A.
  • the following compounds were produced in the manner indicated above.
  • PVC sheets were produced by mixing 100 parts by weight of PVC, 50 parts by weight of plasticisers of varying compositions, and 2 parts by weight of a tin stabiliser and agitating the mixture to a homogeneous paste.
  • This paste was spread as a thin film having a thickness of 1 mm on paper which had been treated with a release agent, whereupon the paste-coated paper was heat- treated in an oven at a temperature of 160°C for 2 min. Having cooled, the plastic sheets were released from the paper.
  • the hydrophilicity of the sheets was determined by measuring, at 20°C, the contact angle obtained between the sheet surface and a water drop when 1 min, 2 min and 4 min had passed since the water drop had been applied. The following results were obtained.
  • PVC produced by suspension polymerisation was dry-mixed in an amount of 100 parts by weight with 0.4 parts by weight of Ca stearate, whereupon 25 parts by weight of dioctyl phthalate, 25 parts by weight of the plasticiser H, 3 parts by weight of epoxidised soybean oil, and 2 parts by weight of barium zinc carboxylate were added, and admixed while heated at 90°C. Then, the mixture was cooled to 30°C and transferred to a rolling mill for PVC, where a film having a thickness of 0.8 mm was produced. Thereafter, the hydrophilicity of the surface was determined as in Example 1. The angles obtained were 53° (1 min), 41° (2 min) and 25° (4 min) .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
PCT/SE1996/001053 1995-09-20 1996-08-27 Diester and the use thereof as hydrophilising agent in pvc WO1997011048A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU71016/96A AU7101696A (en) 1995-09-20 1996-08-27 Diester and the use thereof as hydrophilising agent in pvc

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9503261A SE514045C2 (sv) 1995-09-20 1995-09-20 Användning av en diester som hydrofileringsmedel i PVC, PVC- material, diestrar och framställning av diestrar
SE9503261-1 1995-09-20

Publications (1)

Publication Number Publication Date
WO1997011048A1 true WO1997011048A1 (en) 1997-03-27

Family

ID=20399543

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1996/001053 WO1997011048A1 (en) 1995-09-20 1996-08-27 Diester and the use thereof as hydrophilising agent in pvc

Country Status (3)

Country Link
AU (1) AU7101696A (sv)
SE (1) SE514045C2 (sv)
WO (1) WO1997011048A1 (sv)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19721347A1 (de) * 1997-05-22 1998-11-26 Celanese Gmbh Verfahren zur Herstellung von Esterweichmachern
US9932292B2 (en) 2014-08-01 2018-04-03 Basf Se Process for workup of a crude ester comprising esterification catalyst hydrolysis product in suspended particulate form

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957712A (en) * 1973-08-27 1976-05-18 Henkel & Cie G.M.B.H. Use of a hydrophilic plasticizer for plastic dispersions and pastes
EP0067022A1 (en) * 1981-06-01 1982-12-15 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer film for a laminated glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957712A (en) * 1973-08-27 1976-05-18 Henkel & Cie G.M.B.H. Use of a hydrophilic plasticizer for plastic dispersions and pastes
EP0067022A1 (en) * 1981-06-01 1982-12-15 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer film for a laminated glass

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19721347A1 (de) * 1997-05-22 1998-11-26 Celanese Gmbh Verfahren zur Herstellung von Esterweichmachern
DE19721347C2 (de) * 1997-05-22 2000-03-23 Celanese Chem Europe Gmbh Verfahren zur Herstellung von Esterweichmachern
DE19721347B9 (de) * 1997-05-22 2005-09-29 Celanese Chemicals Europe Gmbh Verfahren zur Herstellung von Esterweichmachern
US9932292B2 (en) 2014-08-01 2018-04-03 Basf Se Process for workup of a crude ester comprising esterification catalyst hydrolysis product in suspended particulate form

Also Published As

Publication number Publication date
AU7101696A (en) 1997-04-09
SE9503261L (sv) 1997-03-21
SE514045C2 (sv) 2000-12-18
SE9503261D0 (sv) 1995-09-20

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