JPH03190885A - Silicate polyol-containing ester polyol composition - Google Patents
Silicate polyol-containing ester polyol compositionInfo
- Publication number
- JPH03190885A JPH03190885A JP32909989A JP32909989A JPH03190885A JP H03190885 A JPH03190885 A JP H03190885A JP 32909989 A JP32909989 A JP 32909989A JP 32909989 A JP32909989 A JP 32909989A JP H03190885 A JPH03190885 A JP H03190885A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- silicate
- ratio
- ester
- produced
- 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.)
- Pending
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 64
- -1 Silicate polyol Chemical class 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 18
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- 239000001361 adipic acid Substances 0.000 abstract description 2
- 235000011037 adipic acid Nutrition 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、シリケートポリオール含有エステルポリオー
ル組成物に関するものである。さらに詳細には、難燃性
、耐熱性のウレタン樹脂の原料等として特に有用なシリ
ケートポリオール含有エステルポリオール組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a silicate polyol-containing ester polyol composition. More specifically, the present invention relates to a silicate polyol-containing ester polyol composition that is particularly useful as a raw material for flame-retardant and heat-resistant urethane resins.
〈従来の技術〉
一般にエステルポリオールは、ウレタン樹脂の原料とし
て使用されている。そしてこれらのウレタン樹脂は難燃
性や耐熱性に優れているため、各種の構造部材や住宅等
の建材用途等に用いられている。<Prior Art> Ester polyols are generally used as raw materials for urethane resins. Since these urethane resins have excellent flame retardancy and heat resistance, they are used for various structural members and building materials such as houses.
〈発明が解決しようとする課題〉
一方、昨今の合成樹脂の難燃性向上に対する強い要求か
ら、ウレタン樹脂に対しても性能向上が求められている
。<Problems to be Solved by the Invention> On the other hand, due to the recent strong demand for improved flame retardancy of synthetic resins, improved performance is also required for urethane resins.
しかし、このエステルポリオールには、粘度が高く取扱
が不便なものがある。However, some of these ester polyols have a high viscosity and are inconvenient to handle.
この粘度問題を解決するために種々の希釈剤および他の
低粘度ポリオールを用いて粘度を低下させることが行な
われているが、反応性、非反応性を問わず、一般にこれ
らの希釈剤や低粘度ポリオールは、得られる成形物の特
性である難燃性や耐熱性を低下させてしまうか、他の物
性、例えば樹脂強度や接着性等を低下させる欠点があっ
た。これらの諸物性を低下させないような物としては、
難燃ポリオール等があるが、これらは一般に粘度が高く
希釈効果が少ない。このためこれらの樹脂の諸物性を低
下させることの無い希釈剤もしくは低粘度ポリオールが
望まれていた。To solve this viscosity problem, various diluents and other low viscosity polyols have been used to lower the viscosity; Viscous polyols have the disadvantage of reducing flame retardancy and heat resistance, which are the characteristics of the resulting molded product, or reducing other physical properties, such as resin strength and adhesiveness. As substances that do not deteriorate these physical properties,
There are flame-retardant polyols, but these generally have high viscosity and little dilution effect. Therefore, a diluent or a low-viscosity polyol that does not deteriorate the physical properties of these resins has been desired.
〈発明が解決しようとする課題〉
本発明は、難燃性、耐熱性を向」二でき、且つ低粘度で
取扱の容易な、樹脂特性を損なうことない樹脂原料の提
供を目的とするものである。<Problems to be Solved by the Invention> The purpose of the present invention is to provide a resin raw material that has improved flame retardancy and heat resistance, has a low viscosity, is easy to handle, and does not impair the resin properties. be.
〈課題を解決するための手段〉
本発明の目的は、テトラアルコキシシランまたは加水分
解率が５０％以下のその加水分解脱水重縮合物（シリケ
ートオリゴマー）を官能基数２のポリオールと反応させ
て得られた水酸基価１００〜１０００のシリケートポリ
オールと水酸基価１５０〜４５０のエステルポリオール
とを１：０．１〜６の重量比で均一混合したシリケート
ポリオール含有エステルポリオール組成物によって達成
される。<Means for Solving the Problems> The object of the present invention is to provide a tetraalkoxysilane or a hydrolyzed and dehydrated polycondensate thereof having a hydrolysis rate of 50% or less (silicate oligomer), which is obtained by reacting with a polyol having two functional groups. This is achieved by using a silicate polyol-containing ester polyol composition in which a silicate polyol having a hydroxyl value of 100 to 1,000 and an ester polyol having a hydroxyl value of 150 to 450 are uniformly mixed in a weight ratio of 1:0.1 to 6.
以下、本発明につき詳細に説明する。Hereinafter, the present invention will be explained in detail.
本発明に使用されるテトラアルコキシシランは、下式で
示される
ＯＲ。The tetraalkoxysilane used in the present invention is OR represented by the following formula.
Ｒ４０−ｓｔ−ＯＲ２
Ｒ３
（ここでＲ５−Ｒ４は、同じであっても異なってもよく
メチル基、エチル基、ブチル基等のアルキル基である。R40-st-OR2 R3 (Here, R5-R4 may be the same or different and are an alkyl group such as a methyl group, an ethyl group, a butyl group, etc.
）
テトラアルコキシシランの加水分解脱水重縮合反応は下
記（Ｉ）式の通りである。即ち、シリケートオリゴマー
の製造はテトラアルコキシシランモノマー中に酸性、中
性あるいはアルカリ性の水を必要量だけ加え反応によっ
て生じるアルコール（加えた水の２倍モル生じる）を除
去することによって行われる。シリケートオリゴマーの
加水分解率とは、（ＩＩ）式に従って計算される値であ
り、求める加水分解率によって加える水の量は決ってく
る。) The hydrolysis, dehydration, and polycondensation reaction of tetraalkoxysilane is as shown in formula (I) below. That is, the production of silicate oligomers is carried out by adding the necessary amount of acidic, neutral or alkaline water to the tetraalkoxysilane monomer and removing the alcohol produced by the reaction (produced twice in mole of the added water). The hydrolysis rate of the silicate oligomer is a value calculated according to formula (II), and the amount of water to be added is determined by the desired hydrolysis rate.
ｍ５ｉ（ＯＲ）４＋ｍｎＨｚｏ→（Ｓｉ（ＯＲ）４−ｚ
ｎｏＩｌ）ｌＩ＋２ｍｎＲＯＨ（１）ｚ
（式中、Ｒはアルキル基を表わし、ｎはＯ〜２の数を表
わす。ｍは整数で、好ましくは２〜約３０である。）
即ち、テトラアルコキシシランの全てのアルコキシ基が
分解したものは加水分解率１００％、２つのアルコキシ
基が分解したものは加水分解率５０％として表す。本発
明では加水分解率０ （すなわちテトラアルコキシシラ
ンモノマー）乃至５０％までのシリケートオリゴマー、
好ましくは加水分解率Ｏ〜３０％、さらに好ましくは０
〜２０％のシリケートオリゴマーが使用される。m5i(OR)4+mnHzo→(Si(OR)4-z
noIl)lI+2mnROH(1)z (In the formula, R represents an alkyl group, and n represents the number of O to 2. m is an integer, preferably 2 to about 30.) That is, all of the tetraalkoxysilanes The hydrolysis rate is expressed as 100% when the alkoxy group is decomposed, and the hydrolysis rate is 50% when two alkoxy groups are decomposed. In the present invention, silicate oligomers with a hydrolysis rate of 0 (i.e., tetraalkoxysilane monomer) to 50%,
Preferably the hydrolysis rate is 0 to 30%, more preferably 0
~20% silicate oligomer is used.
本発明に於て使用される官能基数２のポリオールとして
は、エチレングリコール、ジエチレングリコール、ポリ
エチレングリコール、プロピレングリコール、ジプロピ
レングリコール、ポリプロピレングリコール、ブクンジ
オール、ヘキサンジオール等の多官能アルコールおよび
これらのものにエチレンオキサイド、プロピレンオキサ
イド等のアルキレンオキサイドを付加させたポリオール
等が挙げられる。Polyols having two functional groups used in the present invention include polyfunctional alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, bucundiol, and hexanediol; , polyols to which alkylene oxide such as propylene oxide is added.
これらのポリオールはすべて可燃性物質であり、難燃性
能は有していない。従ってこれらポリオールの分子量は
小さい方がよく、好ましくは６２〜５００さらに好まし
くは６２〜２００である。All of these polyols are flammable substances and do not have flame retardant properties. Therefore, the molecular weight of these polyols is preferably small, preferably from 62 to 500, more preferably from 62 to 200.
テトラアルコキシシランまたはその加水分解脱水重縮合
物とポリオールとの反応は通常のエステル交換反応によ
って行なわれる。すなわち所定量のテトラアルコキシシ
ランまたはその加水分解脱水重縮合物と所定量のポリオ
ールとを反応容器に取り撹拌しつつ約６０〜２００℃に
て反応させアルコールを溜出させて得る。反応は窒素気
流下で行なっても、減圧下で行なっても、常温大気圧下
で行なってもよく、また触媒は使用してもしなくてもよ
く、使用する場合は通常のエステル交換触媒であるアル
キルスズ、酢酸マグネシウム、チタン酸エステル等が使
用できる。The reaction of tetraalkoxysilane or its hydrolyzed, dehydrated polycondensate and polyol is carried out by a conventional transesterification reaction. That is, a predetermined amount of tetraalkoxysilane or its hydrolyzed and dehydrated polycondensate and a predetermined amount of polyol are placed in a reaction vessel and reacted at about 60 to 200° C. with stirring to distill off the alcohol. The reaction may be carried out under a nitrogen stream, under reduced pressure, or at room temperature and atmospheric pressure, and a catalyst may or may not be used. If used, a normal transesterification catalyst is used. Alkyltin, magnesium acetate, titanate, etc. can be used.
テトラアルコキシシランまたはその加水分解脱水重縮合
物とポリオールとの反応割合は、テトラアルコキシシラ
ンまたはその加水分解脱水重縮合物のアルコキシ基とポ
リオールとの当量比で１：０．５〜１０であることが好
ましく、更に好ましくは１：Ｏ，Ｓ〜５である。過剰の
ポリオールはポリイソシアネー１−と反応するが、樹脂
特性の向上には寄与しないので少ない方がよい。得られ
るシリケートポリオールの水酸基価は１００〜１０００
であることが必要であり、好ましくは３００〜７００で
ある。The reaction ratio of the tetraalkoxysilane or its hydrolyzed and dehydrated polycondensate and the polyol shall be 1:0.5 to 10 in equivalent ratio of the alkoxy group of the tetraalkoxysilane or its hydrolyzed and dehydrated polycondensate to the polyol. is preferable, and more preferably 1:O,S~5. Excess polyol reacts with polyisocyanate 1-, but it does not contribute to improvement of resin properties, so the smaller the amount, the better. The hydroxyl value of the obtained silicate polyol is 100 to 1000
, preferably 300 to 700.
本発明に於て使用されるエステルポリオールは、−船釣
にウレタン樹脂分野において使用されている水酸基価が
１５０〜４５０のすべてのエステルポリオールが使用で
きる。これらのエステルポリオールとしては、芳香族、
脂肪族系のエステルポリオールがあり、カルボン酸と多
価アルコールとの反応により得られる。As the ester polyol used in the present invention, all ester polyols having a hydroxyl value of 150 to 450 and used in the field of urethane resins for boat fishing can be used. These ester polyols include aromatic,
There are aliphatic ester polyols, which are obtained by the reaction of carboxylic acids and polyhydric alcohols.
カルボン酸としては、アジピン酸、コハク酸、セバシン
酸、マレイン酸、フタル酸、トリメリット酸、ピロメリ
ット酸、ナフタレンジカルボン酸等およびこれらの酸無
水物があげられ、カルボン酸と反応させる多価アルコー
ルとしてはエチレングリコール、ジエチレングリコール
、トリエチレングリコール、プロピレングリコール、ジ
プロピレングリコール、ブタンジオール、ヘキサンジオ
ール、キシレンジオールや、グリセリン、トリメチロー
ルプロパン等がある。またこれらの多価アルコールにエ
チレンオキザイドやプロピレンオキサイド等のアルキレ
ンオキザイドを付加したポリオールも使用できる。Examples of carboxylic acids include adipic acid, succinic acid, sebacic acid, maleic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, etc., and their acid anhydrides. Examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, xylene diol, glycerin, and trimethylolpropane. Furthermore, polyols obtained by adding alkylene oxide such as ethylene oxide or propylene oxide to these polyhydric alcohols can also be used.
シリケートポリオールとエステルポリオールとの混合割
合は、重量でシリケートポリオールを１とした場合０．
１〜６であることが必要であり、好ましくは１〜４であ
る。エステルポリオールが少なすぎると難燃性、耐熱性
等が悪くなり、多すぎると粘度が高くなり取扱が悪（な
る。またウレタン樹脂等の原料に用いる場合は樹脂物性
等に悪影響を与えない範囲で更に有機溶剤等を添加して
用いても良い。The mixing ratio of silicate polyol and ester polyol is 0.0 when the weight of silicate polyol is 1.
It needs to be 1-6, preferably 1-4. If the amount of ester polyol is too small, flame retardancy and heat resistance will deteriorate, and if it is too large, the viscosity will increase, making handling difficult.Also, when using it as a raw material for urethane resin, etc., it should be used within the range that does not adversely affect the physical properties of the resin. Furthermore, an organic solvent or the like may be added.
かくして得られる本発明のシリケートポリオール含有エ
ステルポリオール組成物は、その構造中に酸化珪素を含
むことからウレタン樹脂等の原料として用いた場合、難
燃性の向上に寄与するばかりでなく、シリケートポリオ
ールは低粘度（数十〜数百Ｃ１）Ｓ／２５℃）であるの
で希釈剤としての機能も有すると考えられる。またシリ
ケートポリオールは活性水素を有することがら、特にウ
レタン樹脂を製造する際にインシアネートと反応し、樹
脂強度等を低下させることばない。Since the silicate polyol-containing ester polyol composition of the present invention thus obtained contains silicon oxide in its structure, when used as a raw material for urethane resins, etc., it not only contributes to improving flame retardancy, but also improves the silicate polyol. Since it has a low viscosity (several tens to hundreds of C1) S/25°C), it is thought to have a function as a diluent. Furthermore, since the silicate polyol has active hydrogen, it does not react with incyanate particularly during the production of urethane resin, thereby causing no reduction in resin strength or the like.
〈実施例〉
本発明のシリケートポリオールエステルポリオール組成
物を実施例により具体的に説明するが、本発明はこれら
の具体例に限定されるものでは−ない。<Examples> The silicate polyol ester polyol composition of the present invention will be specifically explained by examples, but the present invention is not limited to these specific examples.
シリケートポリオール：テトラエチルシリケート１モル
とジエチレングリコール６モルとを、反応容器に取り１
４０℃まで昇温し、生成するエタノールを除去し、水酸
基価６５ｏ、粘度９０ｃｐＳ／２５℃のシリケートポリ
オールを得る。Silicate polyol: 1 mole of tetraethyl silicate and 6 moles of diethylene glycol were placed in a reaction vessel and 1
The temperature is raised to 40°C and the produced ethanol is removed to obtain a silicate polyol having a hydroxyl value of 65o and a viscosity of 90 cpS/25°C.
エステルポリオール：
■ 無水フタル酸とジエチレングリコールから得られる
エステルポリオール、
粘度２２００ ｃ ｐ ｓ ／ ２５℃、水酸基価 １
５
■ ジエチレングリコールとエチレングリコール（モル
比１：１）と、無水フタル酸から得られるエステルポリ
オール、
粘度５８０００ ｃ ｐ ｓ ／ ２５℃、水酸基価０
０
■ 無水フタル酸とエチレングリコールから得られるエ
ステルポリオール、
粘度１２０００００ ｃ ｐ ｓ ／ ２５℃以上、水
酸基価２６０
実施例１
上記シリケートポリオールとエステルポリオールとを混
合する。得られた混合物の外観、粘度を表１に示す。Ester polyol: ■ Ester polyol obtained from phthalic anhydride and diethylene glycol, viscosity 2200 cps/25°C, hydroxyl value 1
5 ■ Ester polyol obtained from diethylene glycol, ethylene glycol (molar ratio 1:1), and phthalic anhydride, viscosity 58000 cps / 25°C, hydroxyl value 0
0 ■ Ester polyol obtained from phthalic anhydride and ethylene glycol, viscosity 1200000 cps/25°C or higher, hydroxyl value 260 Example 1 The above silicate polyol and ester polyol are mixed. Table 1 shows the appearance and viscosity of the obtained mixture.
０
実施例２
実施例１で得た混合物をイソシアネーＩ−とアミン触媒
を用いてウレタン樹脂として硬化させた。0 Example 2 The mixture obtained in Example 1 was cured as a urethane resin using isocyanate I- and an amine catalyst.
イソシアネートとしては、エム・デイ−化成社製“ポリ
メリックＭＤＩ ＰＡＰＩ−１３５″を用い、触媒と
しては、花王社製アミン触媒“カオライザー隘１”を用
いた。イソシアネート／水酸基当量比は１．１５とした
。樹脂製造処方及び得られた樹脂外観を表−２に示す。As the isocyanate, "Polymeric MDI PAPI-135" manufactured by M-D Kasei Co., Ltd. was used, and as the catalyst, "Kaolizer No. 1", manufactured by Kao Corporation, was used as an amine catalyst. The isocyanate/hydroxyl equivalent ratio was 1.15. Table 2 shows the resin manufacturing recipe and the appearance of the resin.
表−２
〈発明の効果〉
本発明のシリケートポリオール含有エステルポリオール
組成物は、ウレタン樹脂等の樹脂原料として用いた場合
その難燃性や耐熱性を向上させる］
だけでなく、高粘度エステルポリオールに対する希釈剤
としても適当であり、極めて有用である。Table 2 <Effects of the Invention> The silicate polyol-containing ester polyol composition of the present invention not only improves flame retardancy and heat resistance when used as a raw material for resins such as urethane resins, but also improves the properties of high-viscosity ester polyols. It is also suitable as a diluent and is extremely useful.
Claims (1)
％以下のその加水分解脱水重縮合物（シリケートオリゴ
マー）を官能基数２のポリオールと反応させて得られた
水酸基価１００〜１０００のシリケートポリオールと水
酸基価１５０〜４５０のエステルポリオールとを１：０
．１〜１：６の重量比で均一混合したシリケートポリオ
ール含有エステルポリオール組成物。(1) Tetraalkoxysilane or hydrolysis rate is 50
A silicate polyol with a hydroxyl value of 100 to 1000 obtained by reacting the hydrolyzed and dehydrated polycondensate (silicate oligomer) with a polyol having a functional number of 2 and an ester polyol with a hydroxyl value of 150 to 450 in a ratio of 1:0.
．． A silicate polyol-containing ester polyol composition uniformly mixed at a weight ratio of 1 to 1:6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32909989A JPH03190885A (en) | 1989-12-19 | 1989-12-19 | Silicate polyol-containing ester polyol composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32909989A JPH03190885A (en) | 1989-12-19 | 1989-12-19 | Silicate polyol-containing ester polyol composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03190885A true JPH03190885A (en) | 1991-08-20 |
Family
ID=18217602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32909989A Pending JPH03190885A (en) | 1989-12-19 | 1989-12-19 | Silicate polyol-containing ester polyol composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03190885A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174967B1 (en) * | 1998-03-20 | 2001-01-16 | Ndsu-Research Foundation | Composition of epoxy resin and (cyclo)alkoxy-substituted organosilane |
| CN112724511A (en) * | 2020-12-22 | 2021-04-30 | 上海日之升科技有限公司 | Easy-to-clean mildew-proof PP composite material and preparation method thereof |
-
1989
- 1989-12-19 JP JP32909989A patent/JPH03190885A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174967B1 (en) * | 1998-03-20 | 2001-01-16 | Ndsu-Research Foundation | Composition of epoxy resin and (cyclo)alkoxy-substituted organosilane |
| US6420494B1 (en) | 1998-03-20 | 2002-07-16 | Ndsu Research Foundation | Curable coating composition with siloxane reactive diluents |
| CN112724511A (en) * | 2020-12-22 | 2021-04-30 | 上海日之升科技有限公司 | Easy-to-clean mildew-proof PP composite material and preparation method thereof |
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