JPS63314233A - Mercaptan-terminated hardenable liquid copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid copolymers of mercaptan-terminated polymers, such as polysulfides, and epoxy-terminated polymers, such as epoxy resins, which can be stored as prepolymers prior to final curing to form a solid product.

The production of resins by co-reaction of polysulfides and polyepoxides in the presence of catalysts is well known. The reaction between the mercaptan groups of polysulfides and the oxirane groups of polyepoxides proceeds readily and is the basis of US-A-2,789,958, which describes the preparation of resinous reaction products of polyepoxides and polysulfides and the process for their preparation. It is. All but one of the examples given in US-A-2,789,958 describe the reaction between a liquid polysulfide and a so-called polyepoxide curing agent in the presence of an amine catalyst. The cured product was a hard, tough, sometimes rubbery material. In another example, a polysulfide polymer was reacted with a polyepoxide curing agent in the absence of an amine catalyst at 70°C for 6 hours and at 25°C for 2 days.

The product was a tough rubbery polymer.

The invention described in US-A-2,789,958 formed the basis for the use of liquid polysulfide polymers as softeners for polyepoxy resins. In these systems, a liquid polysulfide polymer is mechanically mixed with a polyepoxide resin along with a catalyst, usually a tertiary amine. The resulting product is a tough, impact-resistant solid;
If necessary, it can be attached to a wide variety of supports.

The products of such processes have been used in the production of adhesives, paints, electronic encapsulation systems and moldings.

CB-A-787,022 describes self-hardening resins prepared by mixing a liquid or semisolid epoxide resin with a liquid aliphatic saturated polythiopolymercaptan. These resins generally cure to a hard rubbery state within 24 hours, or in some cases 48 hours.

Despite their undoubted success as tough, chemical-resistant paints and adhesives, current LP/epoxy systems
Until the system begins to cure, it is limited by the mercaptan odor emanating from the connected polysulfide components.

US-A-3,101,326 discloses the reaction of polysulfides with styrene oxide to reduce or eliminate mercaptan odor. The products can be used to soften epoxy resins.

According to the present invention, there is provided a curable liquid polymer composition having a stable viscosity before curing, said composition comprising epoxy groups of an epoxy-terminated polymer having at least two epoxy groups per molecule; a copolymer formed by an addition reaction between the mercaptan groups of a mercaptan-terminated polymer having at least two mercaptan groups per polymer, wherein one of said polymers is in stoichiometric excess whereby the composition is Has free epoxy or mercaptan groups.

Mercaptan odor is eliminated in compositions with free epoxy groups.

The present invention also provides a method for preparing said composition, comprising reacting an epoxy-terminated polymer having at least two epoxy groups per molecule with a mercaptan-terminated polymer having at least two mercaptan groups per molecule. wherein one of said polymers is in stoichiometric excess so that the final product has free epoxy or mercaptan groups; and the composition so produced is used to provide a solid copolymer. It can be stored for later curing with curing agents reactive with the epoxy or mercaptan groups.

The basis of the invention is that stable liquid prepolymers can be produced by direct, non-catalytic reaction between liquid polymers with terminal or pendant mercaptan groups and solid or liquid polymers with terminal oxirane groups. The oxirane groups are in stoichiometric excess over the mercaptan groups, or vice versa.

This ensures that the amount of chain extension is limited and therefore the increase in viscosity resulting from the combination of the two polymers is kept to a minimum.

The products of the invention represent a new class of liquid polymeric compositions containing block copolymers with alternating blocks of polysulfides and polyepoxides and having oxirane or mercaptan end groups, depending on the relative proportions of the two components in the initial reaction mixture. . These liquid copolymers can be stored until needed for final curing, at which time the residual reactive groups in the copolymers can participate in further chain extension reactions and are useful commercially available using conventional epoxide or polysulfide curing agents. A series of solid polymers can be produced that have applications.

The products of the invention preferably have a viscosity at 25° C. not higher than 100 Pas, more preferably lower than 60 Pas. Their molecular weight is usually 1,600~s, ooo
, preferably in a range not exceeding 3.000.

The reactions of the invention are preferably carried out at temperatures of 10 to 120°C, conveniently at relatively lower temperatures, such as 10 to 50°C,
This can typically be carried out at 20°C. High reaction temperatures and low viscosities can be obtained using relatively high temperatures, e.g. be done. The reaction mixture can include a solvent.

The compositions of the present invention typically contain as a major component a probe copolymer of epoxy- and mercaptan-terminated polymers.

The ideal structure for a block copolymer is a polysulfide molecule capped with two polyepoxide molecules: H A polyepoxide molecule capped with a ruphide molecule: ScIts-Polysulfide=S-CH2-CH-Polyepoxy structure.

A typical adduct of this type has a molecular weight of about 1,700. Typical polymer compositions of the invention also contain excess polymer in unreacted form.

Slightly less desirable structures for copolymers are: and S-polysulfide polyepoxy polysulfide polyepoxy polysulfide-3H and
00 or higher analogs with molecular weights greater than 0.00 or greater.

The viscosity of the latter analog is greater than that achieved in the ideal structure. The copolymers of the invention do not necessarily have an exclusively ideal structure, but preferred formulations according to the invention provide a predominantly ideal structure in the final product. The invention is not limited to the use of difunctional polysulfide polymers and difunctional polyepoxide polymers, ie, polymers having two functional groups per polymer molecule. Polymers possessing a functionality greater than 2 can also be used to produce liquid products. However, polymers with functionality much greater than 2 will yield solid products or liquid products with high viscosities that are difficult to handle.

Copolymers produced by the chemistry described in this invention are designated as adducts. There are basically two types.
- (i) formed from a stoichiometric excess of oxirane groups over mercaptan groups, the resulting liquid polymer product has residual mercaptan groups, has a mercaptan odor, has free oxirane groups and is an epoxy It can be opened in a chain extension/crosslinking reaction using catalysts commonly used in resin technology. The product in (i) is known as perepoxy adduct.

(ii) formed from a stoichiometric excess of mercaptan groups over oxirane groups. The resulting liquid polymer product has residual oxirane groups, may retain a mercaptan odor, and has free mercaptan groups that are reacted using curing agents commonly used in polysulfide polymer technology, such as manganese dioxide. can be done. (11)
The product in is known as permercaptan adduct.

Compositions containing perepoxy adducts can be used in all technologies that currently use epoxy resins or polysulfides and epoxy resins. Formulation can be simple and curing of the adduct alone can be achieved using catalysts such as tertiary amines,
or, more complexly, with the addition of particulate fillers, chopped fibers, plasticizers, pigments, etc. to the adduct before curing with a catalyst. Perepoxy adducts can also be blended with other liquid polymers, such as polyepoxide polymers, polysulfide polymers, polybutadiene polymers, polybutadiene-coacrylonitrile polymers. Co-reaction with oxirane groups is possible if the polymer has suitable reactive groups, such as carboxylic acids, amines, mercaptans or hydroxyl. With or without co-reaction, the adduct is expected to enhance one or more properties of the second polymer, such as tear strength, adhesion or chemical resistance. Technologies in which liquid adducts can be used include adhesives, paints, paints, electronic encapsulation, encapsulation compounds, moldings, and the production of composites. Permercaptan adducts are currently used with mercaptan polysulfide polymers. Can be used in technology. Curing and crosslinking can be carried out by the use of reagents capable of oxidizing mercaptan groups to disulfide bonds, such as inorganic peroxides, dichromates and permanganates or organic hydroperoxides. It is customary, although not necessary, to form a compound of the liquid polysulfide polymer with particulate optical fibers, plasticizers, thixotropic agents, adhesion promoters, and the like. Similar compounding principles apply to permercaptan adducts. The permercaptan adduct can also be mixed with other liquid polymers, such as polysulfide and polyepoxide polymers, in which case the mercaptan groups in the adduct will co-react with the mercaptan and oxirane groups of the other polymers, respectively. , permercaptan group adducts can also be formulated with high molecular weight solid polysulfide polymers containing co-reacting free mercaptan groups. The addition of adducts to one of these polymers improves one or more properties in the cured product;
For example, it is expected to enhance tear strength, adhesion, elastic recovery and abrasion resistance.

In order for the theory of adduct production to be understood, certain terminology related to epoxy resins and liquid polysulfide polymers must be explained.

Epoxy group content This term is used to mean the number of molecules of epoxide groups in one kilogram of epoxy-terminated polymer.

Units = mol/kg LP Mercaptan Content The 13H mercaptan content of liquid mercaptan-terminated polymers is usually expressed as a percentage. For co-reactions with epoxy-terminated polymers, it is more useful to express the mercaptan content in the same units as the epoxy group content, ie moles/kg.

For example, LP-33 (described in more detail later) is 5.7
It has a mercaptan content of 6%, i.e. LP-331
There are 0.0576 kg of mercaptan groups in kg.

Number of moles of mercaptan per kg = Weight of mercaptan group in 1 kg of polysulfide Molecular weight of mercaptan group Molecule of mercaptan group l = 0.033 kg Therefore, Number of moles of 13H in 1 kg of LP-33 = Mercaptan content of LP-33 = 1.75 mol/kg It has been found that a weight ratio of 1 to 1 gives good results in the case of perepoxy adduct, and that a polyepoxide/polysulfide weight ratio of 2:1 is particularly advantageous from the point of view of low viscosity. was recognized. In general, the proportions are preferably chosen such that the molar ratio of epoxy groups to mercaptan groups is in the range 2:1 to 7.5:1, more preferably 2:1 to 5:1.

A low molar excess of mercaptan groups is generally preferred in the case of perpolysulfide adducts, typically 1.5:1.
~3:1 range. The preferred range for the polysulfide/polyepoxide weight ratio is 3:1 to 6:1.

Mercaptan-terminated polymers usually have a molecular weight of 500 to 1,2000
, preferably having an average molecular weight not exceeding 2.000.

The viscosity is preferably 0.5-2.5 Pas and the mercaptan content is preferably 1.5-2.5 mol/kg
It is.

Mercaptan-terminated polysulfide polymers which are particularly suitable for the purposes of the present invention are characterized by the fact that they have repeating polysulfides between organic groups having at least two primary carbon atoms connected to disulfide bonds. A typical example of a disulfide polymer has the general formula H3-(-R3S
-), -R3H, where R is an organic polyvalent group, preferably primarily a divalent alkylene oxa-hydrocarbon or thia-hydrocarbon group, examples of which are given in US Pat.
No. 789,958, where X is a number greater than 1 and a relatively low number for liquid polymers having a molecular weight of about 500 to 12,000, e.g. 3-1 in some cases
00, to relatively large numbers in the case of solid polymers that can have molecular weights from about ioo, ooo to several million. Low molecular weight polysulfide polymers, e.g. 500-12,000, are typically liquid at 25°C;
Preferably R is an organic dihalide and an inorganic polysulfide with the corresponding backbone, such as NazSy (wherein
y is usually larger than 2).

A solid organic polysulfide polymer can be prepared and cleaved to give a liquid polythiol polymer by the method of U.S. Pat. No. 2,466,963.

Preferred liquid polysulfides used in the preparation of the liquid products of the present invention are manufactured by Morton Thiokol (Morton).
It is manufactured by Th1okol Incorporated and is known as LP. Three brands are particularly exemplified: Ten-1 LP-310000, 94-1, 441, 78-2, 3
32,0LP-3310001,5-201,51-1
,970,5ZL-1400c 1000 0.95
The use of LP-33 in the production of per-epoxy adducts results in adducts with lower and more stable viscosities than those based on LP-3.

This is probably due to the low proportion of trifunctional components present in LP-33 (<0.5% in LP-331);
2% in LP-3). Trifunctionality provides more sites for chain extension and polymer crosslinking by mercaptan-epoxy co-reaction. Cross-linking and chain extension lead to higher adduct molecular weights and therefore higher viscosities.

The use of liquid polysulfides without trifunctionality
It has been shown to yield adducts with lower and more stable viscosities than those based on 3 and LP-33. Z
L-1400c is one suitable "zero-crosslinked" form of LP.

A variety of commercially available epoxy resins can be used as the polyepoxy polymer to make the liquid polymer products of this invention. Although the polyepoxide polymers used are usually liquid, the chemical principles also relate to solid polyepoxide polymers.

Preferred polymers have an average molecular weight of 250-600. The preferred epoxy group content is in the range from 2 to 6 mol/kg. When liquid polymers are used, their viscosity is preferably between 0.5 and 20 Pas. It is formed from shrimp chlorohydrin and bisphenol A.
kote) J and “Araldite (^raldit)
e) Liquid epoxy resins sold under the trade name J are particularly suitable. The properties of some of these epoxides are as follows: It'1l oo's Toro Q ω Locto-1? -11-11-1>B ωωQ ψ Hetotro 5 ki))hehe ゛ゝ鴛ゝHeavy duty industrial epoxy paints are based on solid epoxy resins.These systems are based on solid epoxy resins. Although the solid epoxy paint slightly reduces the flexibility of the cured paint, the liquid Epikote 82
It is said to provide superior corrosion and environmental resistance than Type 8 paints. The present invention contemplates the use of such solid epoxide resins in the formation of stable liquid adducts.

One suitable type of solid epoxy resin that can be used is Shell Epicor 1001, which has a
．． It has an epoxide content of 1 mol/kg.

It is also possible to use low molecular weight polyfunctional glycidyl compounds. These are often referred to as reactive diluents by manufacturers of polyepoxide polymers. One example is Anchar Chemicals.
als ) Heloxy 68,
It has an epoxy equivalent (molar) of 135-155g
mass), with a viscosity of 1-16 mPa5 at 25°C and an average epoxide content of 6.89 mol/kg (
Hewaxy is a registered trademark).

The following examples are presented to more fully illustrate the features of the invention, but are merely illustrative and should not be construed as a limitation on the scope of the invention as defined in the claims.

Example I 200 g of LP-33 was thoroughly mixed with 815.200 g of Epicote. The mixture was left at 25 DEG C. and after one week it was observed that the mercaptan group concentration had fallen to zero as determined by standard analytical procedures and the odor of LP-33 had disappeared. The initial ratio of Epicote 815 to LP-33 represents a 3.0:1 molar ratio of oxirane groups to mercaptan groups.

The viscosity of the product adduct after 2 weeks was 34.9 Pa5 (
25°C). After 6 months storage at room temperature the viscosity was measured again and was shown to be 34.5 Pas (25°C). It was observed that this low viscosity was still maintained after 36 weeks.

100 g of the product adduct was cured with 5 g of the amine tridimethylaminomethylphenol.

The cure properties and physical properties of the cured product were compared to those obtained using 815.50 g of freshly mixed Epicote, 50 g of LP-33, and 5 g of a similar amine curing agent.

The results are shown in Table 3 and show that the cured adduct was LP-33/
It is shown to represent the toughness obtained with the control formulation of Epicote 815.

Gelation time (min) 60 30 Curing heat generation ("C) 40 60 Abrasion resistance "' 8.57 7.21 Tensile strength MP
a) 9.77 10.60 Elongation σ (%) of broken bun 15 25 Impact strength j
2bin) (b' 160+ 160+ Flexibility Possible Hardness Shore D)
59 63(a) DuPont ([)u
Pont) Abrasion tester. Volume ``$i'' per 1000 revolutions (b) Falling weight. 160 Jbin is the maximum value that can be obtained.

Example 2 817.200 g of Epicote was thoroughly mixed with 200 g of LP-3. The mixture was kept at 40 DEG C. and after -weeks the mercabutane level dropped to zero and the LP-3 odor disappeared. The initially taken ratio of Epicote 817 to LP-3 represents a 2.07 to 1 molar ratio of oxirane groups to mercaptan groups. A similar reaction formulation was also kept at room temperature, when the mercaptan content dropped to zero after 3 weeks. The adduct clay formed at room temperature was initially 91. I Pas, 83.9 Pas after 8 weeks and 82.9 Pas after 6 months.
It was I Pas. After 36 weeks, there was little change from this value.

It did not have the odor of LP-3. Viscosity was measured at 25°C. 100 g of the product adduct was cured with 5 g of the amine tridimethylaminomethylphenol. Epicoat 817.50g, LP-33, with a new blend of curing properties.
50 g and that obtained using 5 g of the same amine curing agent.

The results are shown in Table 4.

Gelation time (minutes) 40 30 Curing heat generation ("C) 25 50 Abrasion resistance
8.7 4.7 Tensile strength MPa)
8.32 10.05 Elongation of broken bun (%)
55 95 impact strength/b in)
160+ 160+ Flexibility
Possible Shore D) 5
6 45 Example 3 213.200 g of Epicoat was thoroughly mixed with 200 g of LP-3. The mixture was left at room temperature and after 2 weeks the mercaptan content dropped to zero and the LP-3 odor disappeared. The initially taken ratio of Epicote 213 to LP-3 represents a 2.32 to 1 molar ratio of oxirane groups to mercaptan groups. The viscosity of the adduct when initially formed is 45.6
．． After 04 days when Pas (25℃) it was 41.3
Pas (25°C).

Adducts of Epicote 213 and LP-3 were cured with various levels of tridimethylaminomethylphenol. The results are shown in Table 5.

Table-1] Weight of curing agent (g), weight of 5 10 20 adduct! (g) 100 100 100 Pot life (hours) 1
．． 5 1.0 0.5 Curing heat generation ('C) 2
7 30 34 Clotting time (hours) 6 3
1 hard 3 days, shore D) 35 45
65 Example 4 816.200 g of Epicoat was thoroughly mixed with 200 g of LP-33. The mixture was kept at room temperature and after 16 days the mercaptan content decreased to zero and the LP-33 odor disappeared. The initial ratio of Epicote 816 to LP-33 represents a 2.8 to 1 molar ratio of oxirane groups to mercaptan groups. The viscosity of the adduct when initially formed is 3
1. IPa5 (25°C). After 3 months it was 33.0 Pas (25°C).

Example 5 Araldite 4955.200g was added to LP-33,200
was thoroughly mixed with g. The mixture was left at 40°C. After one week, the mercaptan content decreased to zero and the odor of LP-33 disappeared. The first Araldite 4955 and LP-
The ratio of 3 is 3.2:1 of oxirane groups to mercaptan groups.
means the molar ratio of

The viscosity of the adduct is 4689 Pas when initially formed.
(25°C). After 6 weeks it was 47. lPa5(
25°C).

Example 6 828.250 g of Epicoat was added to 1,000 g of LP-3
mixed with. The mixture was kept at room temperature and the oxirane concentration decreased to zero after 24 weeks. The initial ratio of LP-3 to Epicote 828 represents a 1,62 to 1 molar ratio of mercaptan groups to oxirane groups. The viscosity of the product is 6
It was 6.0 Pas (25°C). 100g of product to 10g of activated manganese dioxide 1 liquid chlorinated paraffin! 2
．． 5 g and 0.5 g of tetramethylthiuram disulfide.
Mixed with 34.5 g of paste consisting of 5 g. The formulation cured to an elastomeric solid in 90 minutes.

Example 7 The following perepoxy adducts were prepared by mixing the liquid polysulfide component and the epoxy resin in a 1:1 weight ratio. 0.4 batches of the system were made and stored at both room temperature and 40°C. Mercaptan content, viscosity and epoxide content of each batch were determined on a weekly basis over a 6 month storage period.

The following room temperature storage perepoxy adducts were found to have stable low viscosities at the end of a 6 month storage period: Epicote 213+LP-3 (approximately 40 Pas) Epicote 213+LP-33 (approximately 30 Pas) Epicote 315+Lp-3 ( Approximately 50 Pas) Epicote 31
5+L, p-33 (approx. 30 Pas) Adducts stored at 40°C with medium heat showed viscosity stability for 17-20 weeks: Epicor) 816+LP-3 (approx. 70Pas) Epicort 816+LP-33 (approx. 40Pas) Epicort 213 Adducts of +r, p-3 and LP-33 stored at 40°C showed viscosity stability for 10-12 weeks, in each case well below 50 Pas.

Example 8 Modification of Epicote 828 with an Epoxy Diluent to Produce a Stable, Low-Viscosity Perepoxy Adduct The following diluents were used: (1) Anchor Chemicals' Helox (Ileox)
y) K116 monofunctional high molecular weight aliphatic glycidyl ether diluent was mixed with Epicote 828 in the following proportions: 828 100 Heroxy MK116 20 (2) Anchor Chemicals Heroxy WC68 Bifunctional Reactive Glycidyl The ether, Heloxy 68, is a technical grade neopentyl glycol diglycidyl ether with low volatility.

The diluent was mixed with Epicote 828 in the following proportions: 1 Rin Epicote 828 100 Heloxy WC6839 Viscosity of modified epoxy resin = IPas The diluent modified Epicote 828 system was mixed with the liquid polysulfide component in a 1=1 weight ratio: Perepoxy adducts were formed: Epicote 828+Heloxy 116+LP-3 Epicote 828+Heloxy 116+LP-33 Epicote 828+Heloxy WC68+LP-33 These adducts were stored at room temperature and 40<0>C.

The following results were obtained.

(1) Store Veloxi 116 samples for up to 17 weeks, and store 35-45 Pas for Epicote 828 + LP-3 modified species.
Range, 25 for Epicote 828+LP-33 variant
It showed a viscosity of ~3QPas.

(2) Epicote 828+Heloxy WC68+LP
Both -33 adduct samples were stable after 10 weeks of storage;
The viscosity of the adduct was very low at 15-25 Pas.

(3) The heloxy 116 sample required 4 weeks of storage to form adducts, whereas the heloxy WC68 sample formed adducts in 2 to 3 weeks.

(4) Both heloxy-modified Epicote 828+LP adducts did not have sufficient storage time to fully evaluate their viscosity stability upon filling.

Example 9 Use of Zero Percent Crosslinked JLP to Produce Stable, Low Viscosity Perepoxy Adduct The zero percent crosslinked LP used in this example was ZL-14.
It was 00G. About ZL-1400G
Morton Thokol Inc.
The analytical data obtained from , USA) is shown below.
The following perepoxy adduct was produced by mixing 400C6,211,82PasZL-1400 and an epoxy resin component in a 1:1 weight ratio: Ebicoat 828+O% crosslinked LP (ZL-1400
C) MY 750+0% crosslinked LP (ZL −
1400C)XD 4955+0% crosslinked L P (
ZL-1400C) MY 778+0% crosslinked L
P (ZL-1400C) "in-house" diluent modified Epicote 828 was also mixed with ZL-1400c in a 1=1 ratio to create an over-engineered Hoxy adduct: Epicote 828+heloxy WC68+O% cross-linked t,p
(ZL-1400C) was manufactured.

Samples were stored at room temperature and 40°C for up to 6 months.

Table 6 clearly shows the effect of mercaptan multifunctionality on adduct viscosity and total viscosity stability for room temperature storage samples.

As a result of the evaluation of the use of zero-crosslinked polysulfides in adduct formation, the following conclusions are drawn: CI) When using zero-crosslinked liquid polysulfides, LP-3, and LP-3
A perepoxy adduct is produced with a lower and more stable viscosity than that prepared from No. 3.

(2) The viscosity and viscosity stability of the adduct are governed by the polysulfide component as follows: Decrease in % trifunctional component Decrease in adduct viscosity Improved viscosity stability Example 10 Epicote 828 and LP-33 Adducts with a 1:0.5 weight blend ratio of 1:0.5 were produced at 150 kg and 50 kg bunch scales to determine whether the properties associated with small scale adduct production in Examples 1-9 are equally applicable to larger production scale quantities. It was measured.

Bulk adduct formulations were made by simply compounding the LP and epoxy components in a steel drum. Bulk formulations were prepared and stored at room temperature.

0.4 kg and 5 kg samples of similar adducts were prepared for comparison.

The bulk adduct production was accompanied by a reaction exotherm which increased the temperature of the formulation from 21'C to 39C, an increase of 18C was observed. This fever is 50kg and 150kg
kg batch, but not detected in the 0.4 kg or 5 kg samples.

The rates of adduct formation for the four batch sizes are shown in Table 7, which shows that the larger the adduct batch size, the faster the rate of adduct formation.

(kg) (days) 0.4 21-28 It was also observed that the bulk adduct exhibited lower storage viscosity and superior viscosity stability when compared to the smaller 0.4 kg batch sample. Table 8 shows these points.

0 5.8 6.8 4.01
54.4 62.2 35.03 46
．． 0 47.3 44.06 49.1
50.6 36.010 '40.8
42.0 45.012 50.6 4
6,2 50.614 38.8 34.
0 53.017 35.9 36.0
53.020 32.6 35.0 23 46.1 45.7 26 43.0 46.5 39 38.0 36.0 Example 11 Adduct of Epicote 1001 and LP-33 in a 1:0.25 weight mixing ratio was manufactured.

The epoxide content of this adduct can be calculated as follows: Epoxide content of Epicote 1001 = 2.1 mol kg
-1 Mercaptan content of LP-33, 1.75 mol, -
1 Therefore, the difference between Epicote 1001 and LP-33 is 0.2
A weight ratio of 5 has excess epoxide in 1.25 kg of sample.

Surplus epoxide is present.

Therefore, 1:0.25 Epicote 1001 + LP-3
Epoxide content of 3 adducts = 1.33 mol kg −1
Solid Epicote 1001 was ground into a fine powder using a mortar and pestle.

Weigh out 50 kg of this powdered resin into a three-day round bottom flask,
12.5 g of LP-33 was added. Approximately Log methyl-ethyl-ketone was added as a solvent and the mixture was thoroughly stirred using a mechanical stirrer.

Heat was applied gradually with a heating mantle. The system became semi-solid when the temperature of the formulation reached 60°C.

At 70°C the formulation was fluid and easily stirred.

The heat source was removed when the temperature of the formulation reached 70°C. The temperature of the formulation continued to rise, peaking at 80°C (this may be due to the reaction exotherm), and then gradually cooled to room temperature.

Virtually all the solvent was removed during the heating step, so that the room temperature formulation was very viscous, but clearly not solid.

After standing at room temperature for 3 days in a closed round bottom flask, the mixture lost its mercaptan odor. Infrared analysis confirmed the absence of mercaptan groups present in the formulation;
It was shown that adducts were formed.

The adduct was then used in the following high solids surface coating formulation: 11 pans 1 F 0.25 wt jf ratio epicor) 1001
+t, P-337 Duct 30-154 Hardener 3 Methyl-Ethyl-Ketone 5 Paint was applied with a doctor blade onto aluminum and shot blasted mild steel plates.

The formulation had the following curing properties: Pot life (38 g cup size) = 1z hours Passive time as thin film on steel = 2-4 hours Example 12 1 of Epicote 1001 and ZL-1400C = 0.25
A weight ratio of the adduct was formulated into a self-pigmented 79% solids solution paint and spray coated onto steel Q-panels and shot blasted mild steel supports. Cold salt spray of cured paint,
Resistance to UV exposure and heat aging was evaluated.

Blend ■ L 1: 0.25 Epicote 1001 + ZL-1400
C100 titanium dioxide 25
Beetle 640 Flow Accelerator 2
0 Ancamfne 1608 Curing agent 4 Methyl-ethyl-ketone: Xylene (1
00:50) 40 Results* Coating appearance = Very high gloss finish Average coating thickness = 150 (1) Cross hatch adhesion BS~3900, Par 1-B6, Cross cut test oo o o.

Excellent Excellent Excellent Excellent (2) Mare resistance, film hardness by ASTM D-3363 pencil test 3) M-plane impact resistance (drop weight method) Salt water spray Salt water spray 70°C, UV 70°C heat aging (
4) Coating film elongation test method using conical mandrel device ASTM D-522 Coating elongation = 30% (5) Corrosion resistance B5-3900. BARTOD 42 There was no evidence of spread of rot, film delamination or blistering after 40 hours of continuous cold salt spray exposure.

Example 13 An epoxy paint composition was prepared using Ebicoat 828/LP-33 adduct as an additive. The formulation was as follows: 11 dishes Epicoat 1001 100 (
1:0.5 Epicote 828 + LP-33) resin
25 Titanium dioxide 15
5 Beetle 640 20 Ancamine 1608 11 Methyl-
Ethyl-ketone: xylene (100:50)
8 3 Cured coating film test results Paint film appearance: High gloss illumination average coating film thickness 8500-800 μm (1) Cross hatch adhesion B S-3900, Part E6, cross cut test Coating film on steel Q panel oo o o.

(Excellent) (2) Membrane hardness by Marresistance ASTM D-3633 pencil test 3)
Back surface impact resistance (4) AST of coating film elongation using conical mandrel device
MD-522 test method Paint film elongation = 13.2% (5) Corrosion resistance B5-3900, Bart F4 No evidence of spread of corrosion, film delamination or blistering after 480 hours of continuous low temperature salt spray exposure Ta.

Example 14 Ebiko 1-1001 and LP-33: 0.2
A 5 weight ratio adduct was evaluated as a primer system for a two part polysulfide sealant on a concrete support. Adduct-based primers were applied onto concrete as a 50% solids solution (formulations are shown below) and the primer/sealant systems were tested for tensile adhesion and cohesion according to B54254.

The primer was made tack-free before applying the polysulfide sealant.

Technical details (1) Primer mixture 1 plate 1: 0.25 Ebico) 1001 + LP-337 duct 100 EDA adduct 870 hardening agent 9
24 Methyl-ethyl-ketone 124 Drying time of brimer system on concrete = 30 minutes*
EDA Adduct 870 hardener is a chemical adduct of a solid epoxy resin with ethylene diamine. The curing agent is manufactured by Anchor Chemical Co.
(UK) Manufactured by Limlted).

Polysulfoxide Sealant System The polysulfide sealant used in this evaluation was a two-component manganese dioxide cured 35% polymer content sealant. Base:Curing paste blending weight ratio is 275722.5
Met.

The results of the B5-425 test are shown in Table 9.

first time! 'J425N -270N 100+++m214
9 N 147 N150 Maximum fracture in χ elongation
NF Mizumanzuke 25N 270N 1001m2
131 N 129 N Maximum failure during 150x elongation NF Heat aging 25N-270N 100 cranes 134N 132N Maximum failure during 100x elongation NF Note NF indicates no failure of adhesion or cohesion.

The initial sealant was heated to 25±2℃・50±5% r, h, before testing.
The tensile stress at 150% strain is shown for a specimen cured for 7 days at .

The tensile stress at 150% strain is shown for specimens fully immersed in water for 7 days at 25±2° C. after an initial water immersion conditioning period.

Heat Aging Tensile stress at 100% strain is shown for specimens heat aged in a ventilated hot air oven at 70±2° C. for 7 days after an initial conditioning period.

These results indicate that the adduct-based brideer allowed the polysulfide sealant to meet the requirements of B5-4254 for tensile adhesion to concrete.

Example 15 Effect of changing the epoxy/LP blend ratio on adduct viscosity Epicote 828 ten zero crosslinked filtered epoxy adducts were prepared with the following epoxy:LP weight blend ratio: Epoxy
10.5 11.3 11.5 The adduct was stored at room temperature and its viscosity was measured on a weekly basis.

Adducts were formed in the t:O,S system after storage for 2 weeks at room temperature. Adduct viscosity after 3 weeks storage is approximately 35 Pas
It was Noma\.

The 1:1 formulation formed adducts after 3 weeks and the viscosity was at a maximum of 80 Pas''? at the time of adduct formation.

The viscosity of the adduct is then approximately 5Q for a remaining shelf life of 21 weeks.
It was stabilized with Pas.

The 1:1.3 formulation system formed adducts after 3 weeks of storage. The viscosity of the adduct peaked at 123 Pas at the time of formation, but then stabilized at 3 QPas. This stability was maintained after 7 weeks of storage.

L: The 1.5 formulation system formed adducts after 4 weeks of storage and had a viscosity of 114 Pas at the time of adduct formation.The resulting adducts did not exhibit viscosity stability.14
After a week the adduct had virtually gelled.

The following conclusions can be drawn from these tests: (1) A reduction in zero-crosslinked LP content results in a lower viscosity perepoxy adduct with improved storage stability.

(2) The less the zero-crosslinked LP component is, the faster the perepoxy adduct is formed.

(3) Zero-crosslinked LP:Epoxy weight ratios greater than 1:1 result in unstable, highly viscous perepoxy adducts.

Adducts with the following epoxy:LP blending ratio of 1:0.5 were also manufactured and stored at both room temperature and 40°C. Their viscosity is measured on a weekly basis: 1:0.5 (epicor) 8
28 + L P -33 (25-40 Pas) 1:
0.5 MY778+LP-33 (20Pas)1
:0.5 MY77B+O% crosslinked L P (15Pa
s) It is meaningful to compare their initial behavior with their 1:1 blended pickles.

1:1 Epicote 828 +LP-33 (70-80
Pa5) 1: I MY 77 B +LP
-33 (30-40Pas) 1:I MY778+O
% crosslinked L P (60 Pas) Obviously the viscosity of the 1:0.5 perepoxy adduct is lower than that of the 1:1 perepoxy adduct at comparable storage times both at room temperature and at 40°C.

Both LP-33 and zero-crosslinked LP in which the epoxy:LP blending ratio is changed from 1=1 to 1:0.5 have the following effects: (a) The viscosity of the resulting per-epoxy adduct is reduced.

(b) Produces a perepoxy adduct with excellent viscosity stability.

Example 16 Cured Adduct 100 of Selected Low Viscosity Hyperepoxy Adduct
5 parts of tridimethylaminomethylphenol curing agent
The following low viscosity adducts were cured using parts by weight.

Epicote 816+LP-3 Epicote 816+LP-33 Epicote 213+LP-3 Ebicor 213+LP-33 Epicote 828+Heloxy 116+LP-3 Epicote 828+Heloxy A C68+LP-33 Table 10 shows gels of these adducts and their regular LP/epoxy equivalents. Compare curing time and curing heat; LP/
The epoxy control was cured with 10 parts by weight of tricmethylaminomethylphenol to 100 parts of the epoxy component.

The results show that the adduct exhibits longer gel time and lower cure exotherm than the LP/epoxy control.

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+1111111 nrinnnnnnr+ shi shi shi shi shi shi shi Ml (+-11-11-11-INN (i) Epicote 815+LP-3, mixed on-site.

(ii) Epicote 815+LP-33, mixed in situ.

(a) The adduct was cured with 5 parts by weight of tridimethylaminoethylphenol per 100 parts of the adduct.

(bl Control was cured with 10 parts by weight of tridimethylaminoethylphenol per 100 parts of epoxy component.

Perepoxy adducts cured with 5 parts by weight of tridimethylaminomethylphenol of the cured perepoxy adducts were then compared to their LP/epoxy controls: (a) Cured hardness b) Abrasion resistance (C1 tensile strength/rupture) Point elongation (d) Flexibility (e) Impact/adhesion comparison results are shown in Tables 11-15.

Boar (a) Curing hardness The hardness values of the adducts are very similar to the control.

(bl Abrasion Resistance The abrasion resistance values of the hardened adducts are generally superior to the control.

(C) Tensile Strength/Elongation at Break The values of the tensile strength and elongation at break of the adduct are determined by their L
lower than the values exhibited by P/epoxy equivalents. This may be due in part to the presence of voids in the adduct specimens.

However, LB-33 based adducts tend to have tensile strength values close to those of the LP-33 based controls.

(dl Flexibility) Both the adduct and control generally have comparable flexibility. Only the Epicote 816+LP-33 adduct is more brittle than its LP/epoxy equivalent.

(e) Impact/Adhesion The impact/adhesion results for the control and adducts are very comparable with the exception of the Epikote 816+LP-33 adduct.

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. nine . 0cocoω circle (((1111 +++ 22 Example 17) The following curing agents were added to perepoxy adducts and their LP/
Both epoxy controls were evaluated.

Anchor 1608 Ancamine 1768 Ancamide (A
ncamide) 502 Ancamine (Anca
The chemistry and levels of each curing agent used to cure the M CA triethylenetetramine adduct and the control are listed in Table 16.

The purpose of the hardener test was: (11) Observation of miscibility of hardener and resin during mixing.

(2) Measurement of gel time, tack-free time, and heat generation of each curing agent/resin system.

(3) Measurement of cured hardness of these systems.

(4) Measurement of the degree of volumetric swelling of the cured product after immersion in water at room temperature and 60°C.

To date, the following adducts and corresponding control resins have been tested: Epicote 816+LP-3 Epicote 816+LP-33 Epicote 213+LP-3 Epicote 213+LP-33 The results of the curing agent tests are shown in Tables 17-28 and are summarized below. . Depending on the required properties, the selection of curing agents is recommended from those tested.

1:1 Epicote 816 + LP-3'M epoxy adduct Optimal adduct/curing agent miscibility Anchor 1608 Ancamine MCA Rapid curing Anchor 1608 Trierlenetetramine Optimal water resistance 60°C immersion Ancamine 1768° Ancamide 502 and triethylenetetramine 22°C immersion Trierlenetetramine 1:1 Epicote 816+LP-33'l! Epoxy Adduct Parameters Optimal Adduct/Curing Agent Miscibility Anchor 1608 Rapid Cure Anchor 1608 Optimum Water Resistance 60°C Soaked Triethylene Tetramine or Ancamine 1768 22°C Soaked Triethylene Tetramine or Ancamine 1768 or Ancamide 502 1 :1 Epicote 213+LP-3'・Eboxy Adduct Parameter-11! ■--Optimal adduct/curing agent miscibility Ancamine 1608 Ancamine MCA Rapid curing Ancamide 1608 Optimum water resistance Ancamide 502 immersed at 60°C or Ancamide 1768 immersed at 22°C in triethylenetetramine 1:1/Epicote 213+LP-3'・Epoxy adduct parameters I E L-
- Optimum adduct/curing agent miscibility Anchor 1608 Ancamide 502 Rapid curing Anchor 1608 Optimal water resistance Triethylenetetramine immersed at 60°C Ancamine 1768 ψ60 C%J Totototoni Kima yo a Fukihama yo Q 8, 8 8 8” ■ Sin Todo Todo: , '1, '1 Δ, X ++'
Brewing! l! ! To to to to to! ts 5hh
hTo2 Example 18 Cured t:o, zs Epicoat 1001 +LP-3
The physical properties of the three adducts were tested. The adduct was evaluated as an unfinished, spatula-applied coating on a shot-blasted mild steel plate. The paint was cured with Ancamine 1608, an aliphatic amine. Regarding the curing characteristics of the paint, two samples were prepared that differed only in the thickness of the near duct coating shown in the following table. Samples were evaluated for adhesion, impact, salt spray and UV resistance. The test results are as follows: Weight l Coating thickness μ) 300-350 110-260 Crosshatch adhesion 00 Back impact (inch bond) >160 >160
Direct impact (inch bond) >160 80UV
Cross hatch adhered after 312 hours of exposure 〇 - Back side impact (
inch bond) 160 - salt spray exposure 2
Cross hatch adhesion after 00 hours 0 Corrosion protection No corrosion spread = No reduction in adhesion = No reduction in flexibility - *Cross hatch adhesion is evaluated on a scale rated from 0 to 6. A reading of 0 means excellent adhesion.

Reading of 6 = Inferior Adhesion Actufacturing 1; 1 Per-Epoxy Adduct Ebicoat 213 + LP-3
Cured samples of 3 and 1:1 Epikote 213+LP-33 controls were subjected to transmission electron microscopy examination of their microstructure.

3 Samples: (a) l:1 Epikote 213 + LP-33 control cured at room temperature with 10 parts by weight of EH-330, (b)
1:1 perepoxy adduct shrimp coat 213 + LP-33 cured at room temperature with 10 parts by weight of EH-330, (C) 1:1 perepoxy adduct shrimp coat cured at 60°C for 1 hour with 10 parts by weight of EH-330 213+
LP-33, was analyzed.

The three samples were expected to exhibit different microstructures due to their different manufacturing methods and curing times.

The test results were as follows: (1) All samples have a microstructure exhibiting a two-phase material.

(2) The dispersed phase, which appears to be LP-33, is the most finely dispersed in the room temperature cured perepoxy adduct sample.

Claims (1)

[Claims] 1. A curable liquid polymer having a stable viscosity before curing, which has the following formula: HABDAH or HABDABDAH (where A is -(SC_2H_4OCH_2OC_2H_4S))
−_a, B is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, C is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, D is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, H is a hydrogen atom, a is an integer of 3 to 7, and b is 1 or 2. 2. A copolymer according to claim 1 having a viscosity at 25° C. of 100 Pas or less. 3. A copolymer according to claim 2 having a viscosity at 25° C. of 60 Pas or less. 4. The copolymer according to claim 1, which has a molecular weight of 1,600 to 5,000. 5. Claim 4, where the molecular weight does not exceed 3000
The copolymer described in section. 6. A curable liquid polymer having a stable viscosity before curing, which has the following formula: HABDAH or HABDABDAH (where A is -(SC_2H_4OCH_2OC_2H_4S)
−_a, B is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, C is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, D is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, H is a hydrogen atom, a is an integer from 3 to 7, and b is 1 or 2) A method for producing a mercaptan end block copolymer represented by the following formula: There are tables, etc. ▼ (However, b is 1 or 2) Epoxy-terminated polymer shown by the following formula: H-(SC_2H_4OCH_2OC_2H_4S)-
A mercaptan-terminated polymer represented by _aH (where a is 3 to 7) is reacted with the epoxy group in the epoxy-terminated polymer/mercaptan group in the mercaptan-terminated polymer at a ratio of less than 1. A method characterized by: 7. The method according to claim 6, wherein the reaction is carried out in the absence of a catalyst. 8. The method of claim 6, wherein the epoxy-terminated polymer has an epoxy content of 2 to 6 moles/kg. 9. The method of claim 6, wherein the epoxy-terminated polymer is a solid. 10. The method of claim 6, wherein the epoxy-terminated polymer has a viscosity of 0.5 to 20 Pas. 11. The average molecular weight of the epoxy-terminated polymer is 250-250.
7. The method of claim 6, wherein the method is 600. 12. The method of claim 6, wherein the mercaptan-terminated polymer is a liquid. 13. The mercaptan-terminated polymer is 0.5-2.5P
7. The method of claim 6, having a viscosity of as. 14. The average molecular weight of the mercaptan-terminated polymer is 50.
7. The method according to claim 6, wherein the number is 0 to 12,000. 15, the mercaptan-terminated polymer has a molecular weight of 500 to 2000
15. The method of claim 14, having an average molecular weight of. 16. The method according to claim 6, wherein the reaction is carried out at 10 to 120°C. 17. The method according to claim 6, wherein the molar ratio of mercaptan groups in the mercaptan-terminated polymer to epoxide groups in the epoxy-terminated polymer is from 1.5:1 to 3:1. 18. The method of claim 6, wherein the copolymer is stored as a pre-cured liquid and then cured with a curing agent to form a solid product.