CA2088610A1 - Process for the preparation of molded products - Google Patents

Process for the preparation of molded products

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Publication number
CA2088610A1
CA2088610A1 CA002088610A CA2088610A CA2088610A1 CA 2088610 A1 CA2088610 A1 CA 2088610A1 CA 002088610 A CA002088610 A CA 002088610A CA 2088610 A CA2088610 A CA 2088610A CA 2088610 A1 CA2088610 A1 CA 2088610A1
Authority
CA
Canada
Prior art keywords
weight
component
polyisocyanate
polyether polyol
nco
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
CA002088610A
Other languages
French (fr)
Inventor
Werner Rasshofer
Christian Weber
Joachim Wagner
Ulrich Liman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of CA2088610A1 publication Critical patent/CA2088610A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C08G18/8019—Masked aromatic polyisocyanates
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Mo3848 LeA 28,866 PROCESS FOR THE PREPARATION OF MOLDED PRODUCTS
ABSTRACT OF THE DISCLOSURE
A process for the preparation of molded products which are particularly readily recyclable. These molded products have a density of from 0.8 to 1.4 g/cm3, and are based on polyurethanes containing urea groups. The process comprises reacting, in one-stage or two-stages via the reaction injection molding technique, a) a polyisocyanate component comprising a polyisocyanate or polyisocyanate blend of the diphenylmethane series, having an NCO functionality of from 2.0 to 2.2, and an NCO content of from 8 to 32 % by weight; b) a polyol comprising at least one polyether polyol having a hydroxyl functionality of 2.5 to 3.5 and a hydroxyl number of from 35 to 50 mg KOH/g, wherein each polyether polyol contains from 5 to 19% by weight, based on the weight of the polyether polyol, of ethylene oxide blocks grafted in the end position; with c) sterically hindered aromatic diamines as chain extenders; in the presence of d) catalysts, and e) from 0.1 to 10% by weight, based on the weight of component b), of additives. In particular, the additives comprise aliphatic polyether amines within the molecular weight range 200 to 800, ethylenediamine propoxylation products with a hydroxyl number in the range of 200 to 1200 mg KOH/g, esterification products of 1,6-hexanediol with ricinoleic acid, or mixtures thereof. The process may also contain other auxiliary substances and additives, such as, for example, milled glass fiber or glass flakes.
Mo3848

Description

~g8~
Mo3848 LeA 28866-U~
PROCESS FOR THE PREPAR~TION OF MQLDED ~RO~DUCTS
BACKG~OUND OF THE INVENTIQN
The invention relates to a novel process for the preparation of molded products based on polyurethanes containing urea groups via the reaction injection molding technique. The process uses selected starting materials which are distinguished by their excellent potential for reuse in the compression molding process while retaining their mechanical properties.
The potential for reuse of used plastics is increasingly becoming a precondition in plastics applications of any kind.
It is already known that molded products prepared via the reaction injection molding technique from polyurethanes containing urea groups, optionally following granulation, may be deformed bycompressionmolding and thus directed and adapted to a new field of application. However, the processes wh;ch have previously been disclosed (e.g. German Offenlegungs-schrift 2,733,755 or German Offenlegungsschrift 3,802,427) have the disadvantage that the molded products deformed via com~ ion molding exhibit mechanical values which are considerably inferior than those of the primary plastics.
Therefore, it was the objective of the invention to discover a novel process for the preparation of molded products based on polyurethanes containing urea groups using the reaction injection molding technique, wherein the process, as a result of the selection of specific starting materials used, yields plastics which may be deformed via thecompressionmolding method without any appreciable loss of mechanical properties.
This would enable the preparation of secondary plastics by compression molding from either the corresponding primary plastics, or the waste products resulting from the preparation of primary plastics. These secondary plastics have mechanical LeA 28 866-US
-2~
properties which are comparable to those of the primary plastics.
The term primary plastics in this context is understood to mean the plastics prepared from the monomer starting materials via the reaction injection molding technique in closed molds.
Secondary plastics are those obtained from primary plastics or from waste products resulting from the preparation of the primary plastics, by compressionmolding~ i.e. by thermal deformation under pressure.
o DESCRIPTION OF THE INVENTION
The subject of the invention relates to a process for the preparation of molded products of polyurethanes containing urea groups having a density of from 0.8 to 1.4 g/cm3, via the one-stage or two-stage reaction injection molding technique.
The process comprises reacting a) a polyisocyanate component comprising a polyisocyanate or polyisocyanate blend of the diphenylmethane series, having an average NCO
functionality of from 2.0 to 2.2, and having a NCO
content of from 8 to 32% by weight, preferably from 18 to 26% by weight;
b) a polyol component comprising at least one polyether polyol having an average hydroxyl functionality of from 2.5 to 3.5, and an average hydroxyl number of from 35 to 50 mg KOH/g, wherein each polyether polyol contains from 5 to 19% by weight, calculated on the weight of the polyether polyol, of ethylene oxide blocks grafted in the end position;
c) from 5 to 100% by weight, calculated on the weight of component b), of a diamine component comprising 1-methyl-3,5-diethyl-2,4-diaminobenzene, or industrial mixtures thereof, with 1-methyl-3,5-diethyl-2,6-diaminobenzene;
d) catalysts which ar~ capable of catalyzing the NCO/OH
addition reaction; and Mo3848 e) a total of frorn 0.1 to 10% by weight, calculated on the weight of component b), of addit;ves compr;s;ng el) aliphatic polyether amines havi~g molecular weights of from 200 to 800, e2) ethylenediamine propoxylation products having a hydroxyl number of from 200 to 1200 mg KOH/g, e3) esterification products of 1,6-hexanediol with ricinoleic acid, or e4~ mixtures thereof;
in a closed mold, while maintaining an NCO index of from 70 to 140.
The polyisocyanate component a) to be used in the process acsording to the invention comprises polyisocyanates or polyisocyanate blends of the diphenylmethane series which have a NCO content of from 8 to 32% by weight, preferably from 18 to 26% by weight, and an average NCO functionality of from 2.0 to 2.2. In particularS 4,4'-diisocyanatodiphenylmethane, liquid blends thereof with 2,4'-diisocyanatodiphenylmethane, and, optionally, 2,2'-diisocyanatodiphenylmethane, and/or with higher homologues thereof containing more than one isocyanate group, and derivatives as obtained by the chemical modification of such polyisocyanates and containing isocyanate groups are considered suitable. Chemical modifications which are particularly suitable are partial carbodiimidization of the isocyanate groups of the polyisocyanates or polyisocyanate blends, and partial urethanization sf the isocyanate groups of the polyisocyanates or polyisocyanate blends. Partial carbodiimidization is described, for example, in U.S. Patent 3,152,162, incorporated herein by reference, and partial 3o urethanization is described, for example, in German Offenlegungsschrift 1,618,380, incorporated herein by reference. Di;socyanates which have been prepared by the reaction with polypropylene glycols having a molecular weight of up to 700 while maintaininy a NCO/OH equivalent ratio of from 3:1 to 10:1 are particularly preferred. Polyisocyanates Mo3848 or polyisocyanate blends of the diphenylmethane series which are liquid at room temperature are preferably used ;n the process according to the invention. It is also possible to use polyisocyanates of the diphenylmethane series which are solid at room temperature, especially solid 4,4'-diisocyanato-diphenylmethane. Howev~r, prepolymers of the polyisocyanate must be used in the process if polyisocyanates of the diphenylmethane series which are solid at room temperature are used.
The polyether polyol component b~ has an average hydroxyl functionality of from 2.5 to ~.5, and an average hydroxyl number of from 35 to 50 mg KOH~g. Component b~ comprises exclusively polyether polyols which contain from 5 to l9~/o by weight, calculated on the total weight of the polyether polyols, of ethylene oxide blocks grafted in the end position.
It is also possible to use polyether polyols which meet this condition and also contain fillers (e.g polymers or polyaddition products) in dispersed form. Suitable polyether polyols b) are described, for example, in U.S. Patent 4,218,543, incorporated herein by reference.
Aromatic diamines of the type described above are considered suitable as component c). These diamines are present in a quantity of from 5 to 100% by weight, preferably from 10 to 35% by weight, calculated on the weight of component b).
Component d) comprises catalysts which are known per se in polyurethane chemistry. The known tin catalysts are especially suitable. Suitable catalysts are described, for example, in U.S. Patent 4,218,543, incorporated herein by reference. The catalysts are generally used in quantities of from 0.01 to 10%
by weight, preferably from 0.05 to 1% by weight, calculated on the weight of component b).
Additives e) which are particularly suitable are those of the type previously described. It is essential that at least one of the additives, el), e2), or e3), as described herein, be Mo3848 ~8~
used in the process according tG the invention. Mixtures or combinations of these additives may, of course, be used. The total quantity of these additives is from 0.1 to 10% by weight, calculated on the weight of component b).
In particular, the aliphatic polyether amines, component el), are aminated polypropylene glycols with;n the molecular weight range of from 200 to 800. These are ava;lable, for example, from Texaco under the trade name Jeffamine.
The propoxylation products of ethylene diamine, component e2), are, in particular, those compounds produced by the addition of from 3 to 6 moles of propylene oxide to 1 mole of ethylene diamine.
The reaction products of 1,6-hexanediol and ricinoleic acid containing ester groups, component e3), are, in particular, those which have an acid number of less than 5 and a hydroxyl number of from 12.5 to 125. These compounds are prepared and used as internal mold release agents according to German Offenlegungsschrift 3,436,163, herein incorporated by reference.
In addition, other auxiliary substances and additives e) may also be used in addition to the aforementioned additives el), e2), and e3), in the process according to the invention.
Suitable optional additives include, for example, milled glass fiber or glass flakes. Quantities of up to 3Q% by weight7 preferably from 10 to 25% by weight, calculated on the total weight of all starting materials a) through e)t of milled glass fiber or glass flakes may be used as fillers or reinforcing agents in the process according to the invention.
The process may, optionally, contain additional auxiliary substances and addit;ves ;nclud;ng, for example, internal mold release agents in quantities of up to 5% by weight, calculated on the weight of component b). One example of a suitable internal mold release agent is zinc stearate.
The process according to the invention is carried out in accordance with the known principles of reaction injection Mo3848 ~ J g ~ ~

molding while maintainin~ a NC0 index of from 70 to 140, preferably from 90 to 125. The NC0 index is the quotient of the number of NC0 groups present in the reaction mixture divided by the number of groups capable of reacting with NC0 groups present ;n the reaction mixture, multiplied by 100. Also, it ;s poss;ble to use either the one-shot process or the two-shot process (;.e. semi-prepolymer principle).
When the one-shot process is used, components b) to e) are combined to form a polyol component, which is then reacted with the polyisocyanate component a) via the reaction injection mold;ng process, ;n accordance w;th the teaching of U.S. Patent 4,218,543.
When the two-shot process is used, at least some of component b) (e.g. 50, 90 or 100 % by weight of component b)), the polyol, is reacted with all of component a), the poly;socyanate, to form a NC0 semi-prepolymer. This NC0 semi-prepolymer is then processed with a mixture of the remaining starting materials and additives in accordance with the principle of reaction injection molding. This two-shot method ;s described ;n princ;ple, for example, in German Patentschrift 3,827,595.
The molded products obtained by the process according to the invention are distinguished from those of the prior art in that they largely retain their excellent mechanical properties after they have undergone further processing or further deformat;on by the extrusion molding method.
All quantitative data in the Examples which follow relate respectively to % by weight and parts by weight.

3o Mo3848 ~8~ J ~

EXAMPLES
Example 1 Preparation of a polyurethane urea component of the prior art (i.e. Comparative Example, not according to the invention).
lA: polvol comDonent 70.12 pàrts of a polyether polyol hav;ng an OH number of 28, and prepared by the propoxylation of trimethylol-propane, followed by the ethoxylation of the propoxylation product (weight ratio of PO:EO = 86.5:13.5), 23.7 parts of a blend of 65% by weight of 2,4-diamino-3,5-diethylbenzene and 35% by weight of 2,6-diamino-3,5-diethylbenzene, 2 parts of a reaction product of ricinoleic acid and 1,6-hexanediol, having an OH number of 35 and containing ester groups, 1 part of triethylenediamine, 0.18 parts of dimethyl tin dilaurate, 0.2 parts of dibutyl tin dilaurate, 0.9 parts of N,N-(bis-3-dimethylamino-propyl) amine, and 1.8 parts of zinc stearate.
lB: isocvanate component (NCO index 110) 60 parts of a semi-prepolymer having an NCO content of 24.5%
by weight, and a viscosity of 500 +/- 100 mPa.s (23C), and prepared by reacting a blend of 90% by weight of 4,4'-diisocyanatodiphenylmethane and 10% by weight of 2,4'-diisocyanatodiphenylmethane, with polypropyleneglycol having an OH number of 515.
Preparation of the RIM components (l-I) The polyol component lA was heated to 45C, the isocyanate component lB was heated to 40C, and both were injected via the reaction injection molding (RIM) process into a tool tempered to 65C having the internal walls coated with an external mold release agent. The plate mold dimensions were380 x 200 x 3 mm.
The specific tool used was a 12 l Rimdomat, manufactured by Hennecke, Birlinghoven. The setting time in the mold was 30 Mo3848 -8- 2~8~
sec, and the pieces were tempered at 120C for 45 min. After storing the molded products (1-I) for 14 days at 20C, the mechanical properties were determined (see Table 1).
Preparation of_the compression molded comp~nents (1-11) The tempered molded components (l-I) were comminuted in a commercially available rotary cutter to form a granulate having particles in which the maximum diameter s ke is 4 mm. ~his granulate was heated for 15 min. in a drying cabinet with air at 180C, and then introduced into a steel she~edge mold which was preheated to 185C, and mounted in a hydraulic press manufactured by Schwabenthan, D-1000 Berlin, model number 300 S.
After charging, the mold was closed and subjected to a load of approx. 300 bar mold pressure (i.e.
specific internal mold pressure) at a continuous molding temperature of 185C. After a pressing time of 3 min., the mold was opened, and the compressedcomponentw~demoldedwhile hot, and then cooled outside the press. After cooling the extrusion molded components (1-II) to 20C, the mechanical properties were determined (see Table 1).
Example 2 Preparation of a polyurethane urea component (i.e.
according to the invention) 2A: Polyol component 70.12 parts of a polyether polyol having an OH number of 44 which was prepared by the propoxylation of trimethylol-propane, followed by the ethoxylation of the propoxylation product (weight rat;o of PO:EO - 86.5:13.5), 23.7 parts of a blend of 65% by weight of 2,4-diamino-3,5-diethylbenzene, and 35% by weight of 2~6-diamino-3,5-diethylbenzene, 2 parts of the reaction product of ricinoleic acid and 1,6-hexanediol, having an OH number of 35 and containing ester groups, 1 part of triethylenediamine, Mo3848 ~88~1~
g 0.18 parts of dimethyl tin dilaurate, 0.2 parts of dibutyl tin dilaurate, 0.9 parts of N,N-(bis-3-dimethylamino-propyl) amine, and 1.8 parts of zinc stearate.
2B: isocYanate component (NCO index 110) 63.6 parts of a semi-prepolymer having an NCO content of 24.5%, and a viscosity SOO +/- 100 mPa.s (23C~, which was prepared by the reaction of a blend of 90% by weight of 4,4'-diisocyanatodiphenylmethane and 10% by weight of 2,4'-diisocyanatodiphenylmethane, with polypropylene-glycol having an OH number of 515.
Preparation of the RIM components (2-I) The polyol component 2A was heated to 45C, the isocyanate component 2B was heated to 40C, and both were injected via the reaction injection molding (RIM) process into a tool tempered to 65C having the internal walls coated with an external mold release agent. The plate mold dimensions were 380 x 200 x 3 mm.
~he specific tool used was a 12 l Rimdomat, manufactured by Hennecke, Birlinghoven. The setting time in the mold was 30 sec, and the pieces were tempered at 120~C for 45 min. After storing the molded products (2-I) for 14 days at 20C, the mechanical properties were determined (see Table 1).
Preparation of the compression molded components (2-II) The tempered molded components (2-I) were comminuted in a commercially available rotary cutter to form a granulate having particles in which the maximum diameter si~e is 4 mm. This granulate was heated for 15 min. in a drying cabinet with air at 180C, and then introduced into a steel she~edge mold which was preheated to 185C, and mounted in a hydraulic press manufactured by Schwabenthan, D-1000 Berlin, model number 300 S.
After charging, the mold was closed and subjected to a load of approx. 300 bar mold pressure (i.e.
specific internal mold pressure) at a continuous molding 3~ temperature of 185C. After a pressing time of 3 min., the Mo3848 2 ~
- lo-mold was opened, and the compressed cornponent w~ demolded w~le hot, and then cooled outside the press. After cooling the compressionmolded components (2-II) to 20C, the mechanical properties were determined (see Table 1).
Example 3 Preparation of a polyurethane urea component (i.e.
according to the invention) This Example demonstrates that it is also possible to use smaller quantities of catalyst.
3A: polvol com~onent 69.9 parts of a polyether polyol having an OH number of 44, which is prepared by propoxylating trimethylolpropane, followed by ethoxylation of the propoxylation product (weight ratio of PO:EO = 86.5:13.5), 23.7 parts of a blend of 65% by weight of 2,4-diamino-3,5-diethylbenzene, and 35% by weight of 2,6-diamino-3,5-diethylbenzene, 2 parts of the reaction product of ricinoleic acid and 1,6-hexanediol, having an OH number of 35 and containing ester groups, 0.7 parts of triethylenediamine, Q.l parts of dimethyl tin dilaurate, 1.8 parts of N,N-(Bis-3-dimethylamino-propyl) amine, and 1.8 parts of zinc stearate.
3B: isocvanate component (NCO index 110) 63.9 parts of a semi-prepolymer having an NCO content of 24.5%
and a viscosity of 500 +/- 100 mPa.s (23C), which was prepared by the reaction of a blend of 90% by weight of 4,4'-diisocyanatodiphenylmethane and 10% by weight of 2,4'-diisocyanatodiphenylmethane, with polypropyleneglycol having an OH number of 515.

Mo3848 Preparation of the RIM components (3-Il The polyol component 3A was heated to 45C, the isocyanate component 3B was heated to 40C, and both were injected via the reaction injection molding (RIM) process into a tool tempered to 65C having the internal walls coated with an external mold release agent. The plate mold dimensions were 380 x 200 x 3 mm.
The specific tool used was a 12 l Rimdomat, manufactured by Hennecke, Birlinghoven. The setting time in the mold was 30 sec, and the pieces were tempered at 120C for 45 min. After lo storing the molded products (3-I~ for 14 days at 20C, the mechanical properties were determined (see Table 1).
Preparation_of the compression molded components (3-II) The tempered molded components (3-I) were comminuted in a commercially available rotary cutter to form a granulate having particl~s in which the maximum diameter size is 4 mm. This granulate was heated for 15 min. in a drying cabinet with air at 180C, and then introduced into a steel shearedge mold which was preheated to 185C, and mounted in a hydraulic press manufactured by Schwabenthan, D-1000 Berlin, model number 300 S.
After charging, the mold was closed and subjected to a load of approx. 300 bar mold pressure (i.e.
specific internal mold pressure) at a continuous molding temperature of 185C. After a pressing time of 3 min., the mold was opened, and the compressedcomponenlwasdemoldedw~le hot, and then cooled outside the press. After cooling the compressionmoldedcomponents (3-II) to 20C, the mechanical properties were determined (see Table 1).

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s c a) ~-- ~ o E c) ~el o ' a~ ., ~ ._ .c, E E Q o ~c o X ~, o o o. ,c ~ ,_ ~._ CS U~ ~ L-l Mo3848 ~8~10 ~able I shows that although both the RIM and the Compression molded components were prepared using the same processing conditions in all three (3) Examples, the RIM materials prepared according to the present invention (i.e. Examples 2 and 3) retain their mechanical properties substantially better following granulation and compression molding than a prior art polyurethane urea material (i.e. Example 1).

Mo3848

Claims (2)

1. A process for the preparation of molded products of polyurethanes containing urea groups having a density of from 0.8 to 1.4 g/cm3 via a one-stage or two-stage reaction injection molding technique, comprising reacting a) a polyisocyanate component comprising a polyisocyanate or polyisocyanate blend of the diphenylmethane series, having an average NCO
functionality of from 2.0 to 2.2, and having a NCO
content of from 8 to 32% by weight;
b) a polyol component comprising at least one polyether polyol having an average hydroxyl functionality of from 2.5 to 3.5, and an average hydroxyl number of from 35 to 50 mg KOH/g, wherein each polyether polyol contains from 5 to 19% by weight, calculated on the weight of the polyether polyol, of ethylene oxide blocks grafted in the end position; and c) from 5 to 100% by weight, calculated on the weight of component b), of a diamine component comprising 1-methyl-3,5-diethyl-2,4-diaminobenzene, or mixtures thereof with 1-methyl-3,5-diethyl-2,6-diaminobenzene, d) catalysts which are capable of catalyzing the NCO/OH
addition reaction; and e) a total of from 0.1 to 10% by weight, based on the weight of component b), of additives comprising e1) aliphatic polyether amines having molecular weight of from 200 to 800, e2) ethylene diamine propoxylation products having a hydroxyl number of from 200 to 1200 mg KOH/g, e3) esterification products of 1,6-hexanediol with ricinoleic acid, or e4) mixtures thereof;
in a closed mold, while maintaining a NCO index of from 70 to 140.

Mo3848
2. The process of Claim 1, wherein component e) additionally comprises up to 30% by weight, based on the total weight of all components a) through e), of milled glass fiber or glass flakes.

Mo3848
CA002088610A 1992-02-05 1993-02-02 Process for the preparation of molded products Abandoned CA2088610A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4203215.6 1992-02-05
DE4203215A DE4203215A1 (en) 1992-02-05 1992-02-05 METHOD FOR PRODUCING MOLDED BODIES

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KR (1) KR930017932A (en)
BR (1) BR9300489A (en)
CA (1) CA2088610A1 (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7750108B2 (en) 2005-04-29 2010-07-06 Dow Global Technologies Inc. Polyester polyols containing secondary alcohol groups and their use in making polyurethanes such as flexible polyurethane foams

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19502969A1 (en) * 1995-01-31 1996-08-01 Elastogran Gmbh Process for the production of rigid polyurethane foams

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3436163A1 (en) * 1984-10-03 1986-04-10 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING MOLDED BODIES
DE3520326A1 (en) * 1985-06-07 1986-12-11 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING ELASTIC MOLDED BODIES
US4758603A (en) * 1987-08-28 1988-07-19 The Dow Chemical Company Dithiocarbamate internal mold release agents
AU640673B2 (en) * 1989-06-16 1993-09-02 Dow Chemical Company, The Process for preparing elastomeric polyurethane or polyurethane-urea polymers, and polyurethanes so prepared

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7750108B2 (en) 2005-04-29 2010-07-06 Dow Global Technologies Inc. Polyester polyols containing secondary alcohol groups and their use in making polyurethanes such as flexible polyurethane foams

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BR9300489A (en) 1993-08-10
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KR930017932A (en) 1993-09-20
MX9300371A (en) 1993-09-01
DE4203215A1 (en) 1993-08-12

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