A one-component light-curing polysulfide sealant

Abstract

The first aspect of this application relates to compositions that are one-component compositions, and wherein the compositions comprise (1) a terminal thiol compound having formula (I); (2) a terminal double bond compound having formula (II); (3) a stabilizer composition, wherein the stabilizer composition comprises an organic acid and a polymerization inhibitor; and (4) a photoinitiator. This application also relates to articles obtained by curing the compositions described in the first aspect of this application, and the use of the compositions described in the first aspect of this application in the preparation of sealants. (I) (II)

Description

Technical Field

[0001] This application belongs to the field of sealing material technology, specifically relating to single-component photocurable polysulfide sealants, and particularly to single-component photocurable polysulfide sealants that can achieve stable coexistence of mercapto and olefin groups. Background Technology

[0002] Polysulfide rubber possesses excellent resistance to various media and extreme temperatures, making it suitable for use as a sealant in aircraft integral fuel tank sealing. In practical applications, sealants are typically used in a two-component form. One component is the base paste, composed of polysulfide rubber compounded with fillers such as calcium carbonate and silica. The other component is a curing agent, primarily composed of manganese dioxide and epoxy resin; alternatively, olefins can be used as curing agents to formulate a cured sealant.

[0003] Traditional UV-cured polysulfide sealants are mostly two-component or multi-component systems, requiring the components to be mixed in specific proportions before vulcanization. This not only makes the weighing and mixing process cumbersome but can also lead to errors in weighing ratios and uneven mixing. Uneven mixing of the sealant affects its curing and sealing performance, thus posing risks to practical applications. In contrast, single-component sealants are gaining increasing popularity due to their ease of use, lack of on-site mixing requirements, and reduced operational errors.

[0004] While single-component polysulfide sealants offer convenience in use, the thiol groups (-SH) and olefins (-C=C) within them are prone to reaction under normal conditions, causing the sealant to cure prematurely during storage and resulting in poor stability.

[0005] In existing technologies, to avoid premature reaction between thiol groups and olefins, thiol groups and olefins are typically placed in different components. However, this cannot meet the requirements of single-component systems. This poses a significant challenge to the development of single-component curable polysulfide sealants. Achieving stable coexistence of thiol groups and olefins has become a critical issue that urgently needs to be addressed in this field.

[0006] Therefore, developing a single-component, photocurable polysulfide sealant that enables the stable coexistence of thiol groups and olefins has significant application value.

[0007] The purpose of this application is to provide a single-component light-curing polysulfide sealant, which uses specific polysulfide ethers and olefins to enable the stable coexistence of thiol groups and olefins in a single component, while ensuring that the sealant can be rapidly cured under light conditions and has excellent sealing performance and storage stability. Summary of the Invention

[0008] The inventors of this application unexpectedly discovered that, by using polysulfide ethers with a specific structure and a specific compounded stabilizer composition, a one-component composition can be obtained that is stable and does not deteriorate during storage, but rapidly cures under light. This composition can be used as a sealant and achieves excellent sealing performance.

[0009] The first aspect of this application relates to a composition, said composition being a one-component composition, and said composition comprising: (1) Compounds with terminal thiol groups of formula (I): (I) in - Each of R1, R2, and R3 independently represents the linear or branched C1 to C2. 20 Alkylene, which is optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - R4 represents the bond or linear or branched C1 to C1. 20 Alkylene, R4 optionally halogenated at one or more positions, C1 to C2 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or optionally, one or more C atoms in R4 are substituted with one or more heteroatoms selected from O, N, and S; - n is an integer from 1 to 50; - m is an integer from 1 to 50; (2) Compounds with terminal double bonds of formula (II): (II) in: - Each R6 independently represents a linear or branched C1 to C2. 100 Alkylene, or residues formed by removing the terminal hydroxyl groups from polyether diols, polyester diols, polycarbonate diols, or polyurethane diols. - Each of X, Q, A, and Z independently represents a bond or a divalent group selected from the following: -O-, -NH-, -S-, , C1 to C 20 Alkylene, wherein Indicates the connection point between the group and the rest of the molecule. - Each R5 and R7 independently represents H, halogen, cyano, or C1 to C2. 20 Alkyl, C1 to C 20Alkyl groups are optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - p is an integer from 1 to 50; (3) A stabilizer composition, wherein the stabilizer composition comprises an organic acid and a polymerization inhibitor; and (4) Photoinitiator.

[0010] The second aspect of this application relates to an article of manufacture obtained by curing a composition as described in the first aspect of this application.

[0011] The third aspect of this application relates to the use of the compositions described in the first aspect of this application in the preparation of sealants. Detailed Implementation

[0012] The "range" disclosed herein is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a specific parameter, it is also expected that ranges of 60 to 110 and 80 to 120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise stated, the numerical range "a to b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 and 5" have been listed in this article; "0 to 5" is just a shortened representation of these numerical combinations. In addition, when a parameter is stated as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0013] Unless otherwise specified, all embodiments and preferred embodiments mentioned in this application can be combined to form new technical solutions.

[0014] Unless otherwise specified, all technical features and preferred features mentioned in this application can be combined to form new technical solutions.

[0015] Unless otherwise specified, all steps mentioned in this application may be performed sequentially or randomly, but sequentially is preferred. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0016] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0017] In this application, unless otherwise stated, "above" and "below" include the stated number, and "several" in "one or more" means two or more.

[0018] In this application, unless otherwise stated, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0019] Unless otherwise specified, percentages (%) or parts refer to weight percentages or parts by weight of the composition.

[0020] Unless otherwise stated herein, the sum of the contents of the components in the composition is 100%.

[0021] Unless otherwise stated herein, the sum of the parts of each component in the composition may be 100 parts by weight.

[0022] In this document, unless otherwise stated, “combination of” means a multi-component mixture of the elements, such as two, three, four, and up to the maximum possible multi-component mixture.

[0023] Unless otherwise specified, the term "a" as used in this specification means "at least one".

[0024] In this paper, unless otherwise stated, all reactions were carried out at room temperature and pressure.

[0025] The first aspect of this application relates to a composition, said composition being a one-component composition, and said composition comprising: (1) Compounds with terminal thiol groups of formula (I): (I) in - Each of R1, R2, and R3 independently represents the linear or branched C1 to C2. 20 Alkylene, which is optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - R4 represents the bond or linear or branched C1 to C1. 20 Alkylene, R4 optionally halogenated at one or more positions, C1 to C2 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or optionally, one or more C atoms in R4 are substituted with one or more heteroatoms selected from O, N, and S; - n is an integer from 1 to 50; - m is an integer from 1 to 50; (2) Compounds with terminal double bonds of formula (II): (II), in: - Each R6 independently represents a linear or branched C1 to C2. 100 Alkylene, or residues formed by removing the terminal hydroxyl groups from polyether diols, polyester diols, polycarbonate diols, or polyurethane diols. - Each of X, Q, A, and Z independently represents a bond or a divalent group selected from the following: -O-, -NH-, -S-, , C1 to C 20 Alkylene, wherein Indicates the connection point between the group and the rest of the molecule; - Each R5 and R7 independently represents H, halogen, cyano, or C1 to C2. 20 Alkyl, C1 to C 20 Alkyl groups are optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - The molar mass of R6 is 100 to 10000 g / mol; (3) A stabilizer composition, wherein the stabilizer composition comprises an organic acid and a polymerization inhibitor; and (4) Photoinitiator.

[0026] Composition

[0027] Terminal thiol compounds

[0028] The composition described in the first aspect of this application comprises a terminal thiol compound having formula (I): (I).

[0029] R1, R2, R3, R4, as well as n and m, are as described above.

[0030] The inventors of this application unexpectedly discovered that using terminal thiol compounds having both -S- and -O- structures can help obtain single-component compositions that are stable and do not deteriorate during storage, but rapidly cure under light.

[0031] According to one embodiment, R1 and R4 may have linear or branched structures. Those skilled in the art can select the structure of R1 and R4 according to the desired composition and article.

[0032] According to a preferred embodiment, R1 and R4 have a branched structure.

[0033] According to a preferred embodiment, R1 and R4 have the following branched structure: ; a, b, and c are each independently selected from integers from 0 to 10, provided that a + b + c is less than or equal to 20.

[0034] In equation (I), R2 and R3 can have linear or branched structures.

[0035] According to a preferred embodiment, R2 and R3 have a linear structure.

[0036] According to a non-limiting embodiment, R2 and R3 may be selected from: methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,7-heptaneene, 1,8-octaneene, 1,9-nonaneene, 1,10-decaneene, 1,11-undecaneene, 1,12-dodecaneene, 1,13-tridecaneene, 1,14-tetradecaneene, 1,14-pentadecaneene, 1,15-hexadecaneene, 1,16-heptadecaneene, 1,17-octadecaneene, 1,18-nonadecaneene, and 1,19-eicosylene.

[0037] In equation (I), n and m represent integers from 1 to 20 independently of each other.

[0038] According to a non-limiting implementation, n and m independently represent 1, or 2, or 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14, or 15, or 16, or 17, or 18, or 19, or 20.

[0039] The molecular weight of the terminal thiol compound of formula (I) described above can be selected and / or adjusted according to the final product, without particular limitation.

[0040] According to one embodiment, the molecular weight of the terminal thiol compound is from 1,000 to 10,000, or from 2,000 to 5,000.

[0041] According to a non-limiting embodiment, the molecular weight of the terminal thiol compound may be 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, or 290. 0, or 3000, or 3100, or 3200, or 3300, or 3400, or 3500, or 3600, or 3700, or 3800, or 3900, or 4000, or 4100, or 4200, or 4300, or 4400, or 4500, or 4600, or 4700, or 4800, or 4900, or 5000, or 5100, or 5200, or 53 00, or 5400, or 5500, or 5600, or 5700, or 5800, or 5900, or 6000, or 6100, or 6200, or 6300, or 6400, or 6500, or 6600, or 6700, or 6800, or 6900, or 7000, or 7100, or 7200, or 7300, or 7400, or 7500, or 7600, or 7 700, or 7800, or 7900, or 8000, or 8100, or 8200, or 8300, or 8400, or 8500, or 8600, or 8700, or 8800, or 8900, or 9000, or 9100, or 9200, or 9300, or 9400, or 9500, or 9600, or 9700, or 9800, or 9900, or 10000.

[0042] In the composition of the first aspect of this application, the terminal thiol compound is present in a mass fraction of 50% to 75% by weight, relative to the total weight of the composition.

[0043] Those skilled in the art will understand that the mass fraction of the terminal thiol compound can be adjusted according to the desired final product.

[0044] According to a non-limiting embodiment, the mass fraction of the terminal thiol compound may be 50 wt%, or 51 wt%, or 52 wt%, or 53 wt%, or 54 wt%, or 55 wt%, or 56 wt%, or 57 wt%, or 58 wt%, or 59 wt%, or 60 wt%, or 61 wt%, or 62 wt%, or 63 wt%, or 64 wt%, or 65 wt%, or 66 wt%, or 67 wt%, or 68 wt%, or 69 wt%, or 70 wt%, or 71 wt%, or 72 wt%, or 73 wt%, or 74 wt%, or 75 wt%, relative to the total weight of the composition.

[0045] Terminal double bond compounds

[0046] As described above, the composition of the first aspect of this application comprises a terminal double bond compound having formula (II): (II).

[0047] X, A, Z, R5, R6, and R7 are as described above.

[0048] According to one embodiment, each of R5 and R7 independently represents H, methyl, or ethyl.

[0049] According to a preferred embodiment, the terminal double bond compound is selected from: , ,or .

[0050] As mentioned above, each R6 independently represents the linear or branched C1 to C2. 100 Alkylene, or residues formed by removing the terminal hydroxyl groups from polyether diols, polyester diols, polycarbonate diols, or polyurethane diols.

[0051] According to a preferred embodiment, R6 is a residue formed by removing the terminal hydroxyl group from a polyether diol.

[0052] According to a preferred embodiment, R6 is a residue formed by removing the terminal hydroxyl group from polyethylene glycol or polypropylene glycol, and the degree of polymerization of the polyethylene glycol or polypropylene glycol is 2 to 100.

[0053] According to one embodiment, the molar mass of R6 is 100 to 2000 g / mol.

[0054] According to non-limiting embodiments, the concentrations are 100 g / mol, or 200 g / mol, or 300 g / mol, or 400 g / mol, or 500 g / mol, or 600 g / mol, or 700 g / mol, or 800 g / mol, or 900 g / mol, or 1000 g / mol, or 1100 g / mol, or 1200 g / mol, or 1300 g / mol, or 1400 g / mol, or 1500 g / mol, or 1600 g / mol, or 1700 g / mol, or 1800 g / mol, or 1900 g / mol, or 2000 g / mol.

[0055] Those skilled in the art can adjust the mass fraction of the terminal double bond compound according to the desired properties of the final product.

[0056] According to one embodiment, the mass fraction of the terminal double bond compound is 15% to 30% by weight, relative to the total weight of the composition.

[0057] According to a non-limiting embodiment, the mass fraction of the terminal double bond compound is 15 wt%, or 16 wt%, or 17 wt%, or 18 wt%, or 19 wt%, or 20 wt%, or 21 wt%, or 22 wt%, or 23 wt%, or 24 wt%, or 25 wt%, or 26 wt%, or 27 wt%, or 28 wt%, or 29 wt%, or 30 wt%, relative to the total weight of the composition.

[0058] stabilizer composition

[0059] The composition described in the first aspect of this application comprises a stabilizer composition, wherein the stabilizer composition comprises an organic acid and a polymerization inhibitor.

[0060] Those skilled in the art will find, unexpectedly, that the compositions described in the first aspect of this application can remain stable during storage when using stabilizer compositions comprising both organic acids and polymerization inhibitors.

[0061] Neither the organic acids nor the polymerization inhibitors that can be used in the stabilizer composition are particularly limited.

[0062] According to one embodiment, the organic acid is selected from one or more of the following: (meth)acrylic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, lactic acid, benzoic acid, phenylacetic acid, salicylic acid, methylbenzoic acid, tert-butylbenzoic acid, and naphthoic acid.

[0063] According to the embodiments described, the polymerization inhibitor may be selected from one or more of the following: - Phenolic polymerization inhibitors, such as hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-p-cresol (BHT), tert-butylhydroquinone (TBHQ), and p-tert-butylcatechol (TBC). - Quinone polymerization inhibitors, such as p-benzoquinone, tetrachlorobenzoquinone, and 1,4-naphthoquinone; - Amine polymerization inhibitors, such as N,N'-di-sec-butyl-p-phenylenediamine (DBPPD), phenothiazine (PTZ), and triethylamine; - Inorganic salts, such as copper sulfate, ferrous sulfate, and sodium nitrosoferricyanide.

[0064] Those skilled in the art can adjust the mass fraction of the stabilizer composition in the composition described in the first aspect of this application according to the desired properties of the final product.

[0065] According to one embodiment, the stabilizer composition has a mass fraction of 0.4% to 1.0% relative to the total weight of the composition.

[0066] According to a non-limiting embodiment, the stabilizer composition is expressed in the following mass fractions: 0.40 wt%, or 0.45 wt%, or 0.50 wt%, or 0.55 wt%, or 0.60 wt%, or 0.65 wt%, or 0.70 wt%, or 0.75 wt%, or 0.80 wt%, or 0.85 wt%, or 0.90 wt%, or 0.95 wt%, or 1.00 wt%, relative to the total weight of the composition.

[0067] According to one embodiment, in the stabilizer composition, the mass ratio of organic acid to polymerization inhibitor is 0.8:1 to 2:1, or 1:1 to 1.5:1. However, those skilled in the art will recognize that the mass ratio of organic acid to polymerization inhibitor in the stabilizer composition is not particularly limited, but can be selected according to the desired properties of the final product.

[0068] According to a limited embodiment by Yifei, the mass ratio of the organic acid to the polymerization inhibitor can be 0.80:1, or 0.82:1, or 0.84:1, or 0.86:1, or 0.88:1, or 0.90:1, or 0.92:1, or 0.94:1, or 0.96:1, or 0.98:1, or 1.00:1, or 1.02:1, or 1.04: 1, or 1.06:1, or 1.08:1, or 1.10:1, or 1.12:1, or 1.14:1, or 1.16:1, or 1.18:1, or 1.20:1, or 1.22:1, or 1.24:1, or 1.26:1, or 1.28:1, or 1.30:1, or 1.32:1, or 1.34:1, or 1.36:1 Or 1.38:1, or 1.40:1, or 1.42:1, or 1.44:1, or 1.46:1, or 1.48:1, or 1.50:1, or 1.52:1, or 1.54:1, or 1.56:1, or 1.58:1, or 1.60:1, or 1.62:1, or 1.64:1, or 1.66:1, or 1.68:1 Or 1.70:1, or 1.72:1, or 1.74:1, or 1.76:1, or 1.78:1, or 1.80:1, or 1.82:1, or 1.84:1, or 1.86:1, or 1.88:1, or 1.90:1, or 1.92:1, or 1.94:1, or 1.96:1, or 1.98:1, or 2.00:1.

[0069] Photoinitiator

[0070] As described above, the composition described in the first aspect of this application comprises a photoinitiator.

[0071] According to one embodiment, the photoinitiator used in the composition described in the first aspect of this application is selected from one or more of the following: - Benzoin derivatives, such as benzoin, dimethyl benzoate, ethyl benzoate, isopropyl benzoate, and butyl benzoate; - Benzophenones, such as benzophenone, 4-methylbenzophenone, 2-hydroxybenzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0072] The amount of photoinitiator can be adjusted and / or selected according to the desired properties of the final product, as will be clear to those skilled in the art.

[0073] According to one embodiment, the photoinitiator has a mass fraction of 0.5% to 0.85% relative to the total weight of the composition.

[0074] According to a non-limiting embodiment, the photoinitiator may be present in a mass fraction of 0.50 wt%, 0.55 wt%, 0.60 wt%, 0.65 wt%, 0.70 wt%, 0.75 wt%, 0.80 wt%, or 0.85 wt%, relative to the total weight of the composition.

[0075] Photoalkali-producing agent

[0076] According to a preferred embodiment, the composition further comprises a photoalkali-generating agent.

[0077] The photo-alkali-producing agent can generate basic compounds, such as tertiary amines, under light conditions.

[0078] According to a non-limiting embodiment, the photobase generator PBG is selected from quaternary ammonium salt photobase generators, such as TBD·HBPh4, tetrabutylammonium phenylacetate, benzyltrimethylammonium phenyl glycolate, tetramethylammonium naphthate, o-nitrobenzyltrimethylammonium chloride, o-nitrobenzyltrimethylammonium bromide, and bis-o-nitrobenzyldimethylammonium hexafluorophosphate.

[0079] According to one embodiment, the mass fraction of the photoalkali-generating agent is 0.3% to 1% by weight, relative to the total weight of the composition.

[0080] For example, the mass fraction of the photoalkali-generating agent may be 0.30 wt%, or 0.35 wt%, or 0.40 wt%, or 0.45 wt%, or 0.50 wt%, or 0.55 wt%, or 0.60 wt%, or 0.65 wt%, or 0.70 wt%, or 0.75 wt%, or 0.80 wt%, or 0.85 wt%, or 0.90 wt%, or 0.95 wt%, or 1.00 wt%, relative to the total weight of the composition.

[0081] Tackifier

[0082] According to a preferred embodiment, the composition described in the first aspect of this application further comprises a tackifier.

[0083] According to one embodiment, the tackifier comprises an acrylate silane coupling agent and a mercapto silane coupling agent, wherein the acrylate silane coupling agent has the following structure:

[0084] The mercapto-based silane coupling agent has the following structure:

[0085] Where R8 is -H or -CH3, R9 and R10 Each can be independently -CH3 or -CH2CH3. x and y are each independently between 1 and 3. Groups d and e can be independently scored from 1 to 5. In embodiments of the tackifier, the molar ratio of the acrylate silane coupling agent to the mercapto silane coupling agent is from 1:0.5 to 1:1.5.

[0086] For example, the molar ratio of the acrylate silane coupling agent and the mercapto silane coupling agent may be 1:0.50, or 1:0.55, or 1:0.60, or 1:0.65, or 1:0.70, or 1:0.75, or 1:0.80, or 1:0.85, or 1:0.90, or 1:0.95, or 1:1.00, or 1:1.05, or 1:1.10, or 1:1.15, or 1:1.20, or 1:1.25, or 1:1.30, or 1:1.35, or 1:1.40, or 1:1.45, or 1:1.50.

[0087] However, those skilled in the art will know that the molar ratio of the acrylate silane coupling agent and the mercapto silane coupling agent in the tackifier can be selected in other proportions and is not particularly limited.

[0088] According to one embodiment, the tackifier has a mass fraction of 1.0% to 1.5% by weight, relative to the total weight of the composition.

[0089] For example, the mass fraction of the tackifier may be 1.00 wt%, or 1.05 wt%, or 1.10 wt%, or 1.15 wt%, or 1.20 wt%, or 1.25 wt%, or 1.30 wt%, or 1.35 wt%, or 1.40 wt%, or 1.45 wt%, or 1.50 wt%, relative to the total weight of the composition.

[0090] plasticizer

[0091] According to a preferred embodiment, the composition described in the first aspect of this application further comprises a plasticizer.

[0092] According to one embodiment, the plasticizer is selected from one or more of the following: butyl benzyl phthalate, dibutyl phthalate, or chlorinated paraffin.

[0093] According to one embodiment, the plasticizer has a mass fraction of 1% to 5% by weight, relative to the total weight of the composition.

[0094] According to a non-limiting embodiment, the mass fraction of the plasticizer may be 1 wt%, or 1.5 wt%, or 2.0 wt%, or 2.5 wt%, or 3.0 wt%, or 3.5 wt%, or 4.0 wt%, or 4.5 wt%, or 5.0 wt%.

[0095] filler

[0096] According to a preferred embodiment, the composition described in the first aspect of this application further comprises a filler.

[0097] According to one embodiment, the filler is selected from fumed silica.

[0098] According to one embodiment, the filler has a mass fraction of 1% to 15% by weight, relative to the total weight of the composition.

[0099] As described above, by using polysulfide ethers with specific structures and specific compounded stabilizer compositions, a one-component composition that is stable and does not deteriorate during storage, but cures rapidly under light exposure, can be obtained. This composition can be used as a sealant and achieves excellent sealing performance.

[0100] According to one embodiment, the viscosity of the composition described in the first aspect of this application increases by less than 10% during a 6-month storage period, for example, less than 9%, or 8%, or 7%, or 6%, or 5%, or 4%, or 3%, or 2%, or 1%.

[0101] Products

[0102] The second aspect of this application relates to articles obtained by curing the composition described in the first aspect of this application.

[0103] Mechanical properties

[0104] According to one embodiment, the tensile strength of the article is greater than 1 MPa, for example greater than 1.0 MPa, or 1.1 MPa, or 1.2 MPa, or 1.3 MPa, or 1.4 MPa, or 1.5 MPa, or 1.6 MPa, or 1.7 MPa, or 1.8 MPa, or 1.9 MPa, or 2.0 MPa, or 2.1 MPa, or 2.2 MPa, or 2.3 MPa, or 2.4 MPa, or 2.5 MPa, or 2.6 MPa, or 2.7 MPa, or 2.8 MPa, or 2.9 MPa, or 3.0 MPa.

[0105] The tensile strength can be measured according to the standard GB / T528-2009 "Test methods for tensile properties of rubber, thermoplastic rubber and rubber products".

[0106] According to an embodiment of the second aspect of a patent application, the elongation at break of the article is greater than 100% or greater than 150%.

[0107] For example, the elongation at break of the article is greater than 100%, or 110%, or 120%, or 130%, or 140%, or 150%, or 160%, or 170%, or 180%, or 190%, or 200%, or 210%, or 220%, or 230%, or 240%, or 250%, or 260%, or 270%, or 280%, or 290%, or 300%, or 310%, or 320%, or 330%, or 340%, or 350%.

[0108] Mechanical property retention rate

[0109] The article described in the second aspect of this application can retain its mechanical properties even after aging.

[0110] The aging process can be carried out, for example, by spraying a 5% NaCl solution at 35°C.

[0111] According to one embodiment, the tensile strength retention rate of the article is greater than 80% after aging for 1000 hours.

[0112] The retention rate of tensile strength can be obtained by comparing the tensile strength after aging with the tensile strength before aging.

[0113] For example, after 1000 hours of aging, the tensile strength retention rate of the article may be 80%, or 81%, or 82%, or 83%, or 84%, or 85%, or 86%, or 87%, or 88%, or 89%, or 90%, or 91%, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%, or 98%, or 99%.

[0114] According to one embodiment, the article retains more than 80% of its elongation at break after aging for 1000 hours.

[0115] The retention rate of elongation at break can be obtained by comparing the elongation at break after aging with the elongation at break before aging.

[0116] For example, after 1000 hours of aging, the elongation at break of the article can be 80%, or 81%, or 82%, or 83%, or 84%, or 85%, or 86%, or 87%, or 88%, or 89%, or 90%, or 91%, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%, or 98%, or 99%.

[0117] According to one embodiment, after the product is soaked in No. 3 kerosene at 60°C for 7 days, the weight change rate is -5% to 5%.

[0118] The rate of change of weight can be calculated as follows: Weight change rate = [(mass after soaking) / (mass before soaking) - 1] 100% According to a non-limiting embodiment, after the article was soaked in No. 3 kerosene at 60°C for 7 days, the weight change rate was -5.0%, or -4.8%, or -4.6%, or -4.4%, or -4.2%, or -4.0%, or -3.8%, or -3.6%, or -3.4%, or -3.2%, or -3.0%, or -2.8%, or -2.6%, or -2.4%, or -2.2%, or -2.0%, or -1.8%, or -1.6%, or -1.4%, or -1.2%, or -1.0%. Or -0.8%, or -0.6%, or -0.4%, or -0.2%, or 0.0%, or 0.2%, or 0.4%, or 0.6%, or 0.8%, or 1.0%, or 1.2%, or 1.4%, or 1.6%, or 1.8%, or 2.0%, or 2.2%, or 2.4%, or 2.6%, or 2.8%, or 3.0%, or 3.2%, or 3.4%, or 3.6%, or 3.8%, or 4.0%, or 4.2%, or 4.4%, or 4.6%, or 4.8%, or 5.0%.

[0119] use

[0120] According to a third aspect of this application, this application relates to the use of the composition described in the first aspect of this application in the preparation of a sealant.

[0121] According to one embodiment, the composition has a wavelength of 365 nm and an intensity of 80 mW / cm. 2 Under ultraviolet light irradiation, it is completely cured within 60 seconds. For example, when the composition of the first aspect of this application is irradiated with ultraviolet light at a wavelength of 365 nm and an intensity of 80 mW / cm², it is completely cured. 2 When irradiated with ultraviolet light, the composition is completely cured within 60 seconds, or 55 seconds, or 50 seconds, or 45 seconds, or 40 seconds.

[0122] Complete curing can be determined by whether the hardness of the resulting sealant reaches a stable value. Specifically, it is measured periodically using a Shore A hardness tester. When the hardness value no longer increases significantly over time, it indicates that the curing reaction of the sealant is basically complete.

[0123] Example

[0124] This application will now be described in more detail with reference to the following embodiments. It should be understood that the described embodiments are for further illustrating the invention and should not be construed as limiting the scope of protection of the invention.

[0125] The reagents used in the examples are summarized in Table 1 below: Table 1. Reagents used in the examples

[0126] Polysulfide #1 has the following structure: HS-CH(CH3)-(CH2)2-S-[(-CH2-)2-O-(-CH2-)2-S] n -(CH2)2-CH(CH3)-SH Polysulfide #2 has the following structure: HS-CH(CH3)-(CH2)3-S-[(-CH2-)3-O-(-CH2-)2-S] n -(CH2)3-CH(CH3)-SH Polysulfide #3 has the following structure: HS-CH-(CH2)2-S-[(-CH2-)2-O-(-CH2-)2-S] n -(CH2)2-CH-SH The effective structure of vinyl-terminated polyether #1 is diethylene glycol methacrylate; The effective structure of the terminal vinyl polyether #2 is polypropylene glycol methacrylate.

[0127] The tests in this application embodiment are performed using the following methods or standards: Tensile strength and elongation at break were measured in accordance with the standard GB / T528-2009 "Test methods for tensile properties of rubber, thermoplastic rubber and rubber products".

[0128] Curing performance: The compositions from the examples and comparative examples were coated onto a glass substrate and cured at a wavelength of 365 nm and an intensity of 80 mW / cm². 2 Cured under ultraviolet light.

[0129] Weather resistance: The cured samples were placed in an artificial climate aging test chamber for 1000 hours of aging, and then the tensile strength and elongation at break of the aged samples were tested. The aging was carried out by spraying a 5% sodium chloride (NaCl) solution at 35°C.

[0130] Chemical resistance: The cured sample was immersed in No. 3 kerosene at 60°C for 7 days. The sample was observed to see if it swelled and cracked, and the weight change rate of the sample was measured.

[0131] Various embodiments

[0132] Example 1

[0133] (1) Mix methacrylic acid and hydroquinone at a mass ratio of 1:1 and then place them in an oven at 60°C for 12 hours to obtain a stabilizer composition.

[0134] (2) KH570 and KH590 were mixed in a molar ratio of 1:1, and then 0.05% by weight of AIBN was added relative to the mixture of KH570 and KH590. After mixing evenly, the mixture was placed in an oven at 80°C for 6 hours to obtain the thickener.

[0135] (3) Take 70g of polysulfide #1, 20g of diethylene glycol methacrylate, 10g of fumed silica, 0.8g of the stabilizer composition obtained in (1), 0.8g of benzoin, 0.8g of photoalkali-generating agent TBD·HBPh4, 1.5g of the tackifier obtained in (2), and 3g of dibutyl phthalate, mix them evenly to obtain the composition described in the first aspect of this application.

[0136] Example 2

[0137] (1) Stearic acid and p-tert-butylcatechol were mixed evenly at a mass ratio of 1:1, and then placed in an oven at 60°C for 12 hours to obtain a stabilizer composition.

[0138] (2) KH570 and KH590 were mixed in a molar ratio of 1:1, and then 0.04% by weight of AIBN was added relative to the mixture of KH570 and KH590. After mixing evenly, the mixture was placed in an oven at 80°C for 7 hours to obtain the thickener.

[0139] (3) Take 60g of polysulfide #2, 25g of dipropylene glycol methacrylate, 12g of fumed silica, 0.6g of the stabilizer composition obtained in (1), 0.6g of 2,4-dihydroxybenzophenone, 0.6g of photoalkali-generating agent TBD·HBPh4, 1.5g of the tackifier obtained in (2), and 5g of butyl benzyl phthalate, mix them evenly to obtain the composition described in the first aspect of this application.

[0140] Example 3

[0141] Example 1 was repeated, except that the mass ratio of methacrylic acid and hydroquinone in step (1) was 1.2:1.

[0142] Example 4

[0143] Example 1 was repeated, except that the mass ratio of methacrylic acid and hydroquinone in step (1) was 0.8:1.

[0144] Example 5

[0145] Repeat Example 1, except that no photoalkali-producing agent is used.

[0146] Example 6

[0147] Example 1 was repeated, except that the general structural formula of the polysulfide was the same as that of polysulfide #1, but the number average molecular weight was 7000.

[0148] Example 7

[0149] Example 1 was repeated, except that the general structural formula of the polysulfide was the same as that of polysulfide #1, but the number average molecular weight was 2000.

[0150] Example 8

[0151] Example 1 was repeated, except that end-vinyl polyether #1 was used instead of diethylene glycol methacrylate.

[0152] Example 9

[0153] Example 1 was repeated, except that 2,4-dihydroxybenzophenone was used instead of benzoin.

[0154] Each pair of proportions

[0155] Comparative Example 1

[0156] Repeat Example 1, except that: - Skip step (1), i.e. do not use the stabilizer composition described in the first aspect of this application; - The tackifier used is: KH570; - The following raw materials are used in step (3): 100g of polysulfide #3, 30g of vinyl-terminated polyether #1, 1.5g of photoinitiator 2,4-dihydroxybenzophenone, 10g of fumed silica, 10g of talc, 5g of dibutyl phthalate, and 1g of tackifier.

[0157] Comparative Example 2

[0158] Repeat Example 1, except that: - Skip step (1), i.e. do not use the stabilizer composition described in the first aspect of this application; - The tackifier used is: KH590; - The following raw materials are used in step (3): 100g of thiol-containing polysulfide polymer, 30g of vinyl-terminated polyether #2, 2g of benzoin ether, 20g of talc, and 5g of dibutyl phthalate.

[0159] Comparative Example 3

[0160] Repeat Example 1, except that only methacrylic acid is used in step (1).

[0161] Comparative Example 4

[0162] Repeat Example 1, except that only hydroquinone is used in step (1).

[0163] Comparative Example 5

[0164] Repeat Example 1, except that in step (3), polysulfide #1 is replaced with a polysulfide that does not contain -O- in the main chain.

[0165] Comparative Example 6

[0166] Repeat Example 1, except that in step (3), the polysulfide #1 is replaced with a polyether that does not contain -S- in the main chain.

[0167] Comparative Example 7

[0168] Repeat Example 1, except that no tackifier is used.

[0169] result

[0170] The test results of the compositions of the first aspect of this application obtained in each embodiment and comparative example are summarized in Tables 2-4.

[0171] Table 2 Storage stability results Store at 25°C for 6 months Table 3 Mechanical properties and weather resistance

[0172] Table 4 Chemical Resistance

[0173] The articles in Examples 1-9 were prepared according to the method of this application. Specifically, Examples 1-9 used the composition as described in the first aspect of this application, wherein a stabilizer composition and a terminal thiol compound having both -S- and -O- structures were used.

[0174] As mentioned above, the applicant unexpectedly discovered that the compositions in Examples 1-9 were stable and did not deteriorate during storage, but cured rapidly under light. The cured products exhibited good mechanical properties and weather resistance, and showed no significant swelling or cracking after being immersed in kerosene for seven days, with a weight change rate of less than 3%. Furthermore, the tensile strength and elongation at break of the products obtained after aging tests remained above 85%.

[0175] Furthermore, the applicant also discovered through comparisons 1-7 that: (1) When using a single coupling agent as a thickener, it cannot be stored stably and becomes significantly thickened and completely gelled after 2-3 weeks of storage. (2) If a polyether without -S- in the main chain is used, the composition also cannot achieve stable storage. The comparison composition thickened significantly and completely gelled after 2 weeks of storage.

[0176] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be considered as limitations on the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. For those skilled in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A composition, said composition being a one-component composition, and said composition comprising: (1) Compounds with terminal thiol groups of formula (I): (I) in - Each of R1, R2, and R3 independently represents the linear or branched C1 to C2. 20 Alkylene, which is optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - R4 represents the bond or linear or branched C1 to C1. 20 Alkylene, R4 optionally halogenated at one or more positions, C1 to C2 12 Alkyl, or C1 to C 12 Alkoxy substitution, and / or optionally one or more C atoms in R4 are substituted with one or more heteroatoms selected from O, N, and S; - n is an integer from 1 to 50; - m is an integer from 1 to 50; (2) Compounds with terminal double bonds of formula (II): (II) in: - Each R6 independently represents a linear or branched C1 to C2. 100 Alkylene, or residues formed by removing the terminal hydroxyl groups from polyether diols, polyester diols, polycarbonate diols, or polyurethane diols. - Each of X, Q, A, and Z independently represents a bond or a divalent group selected from the following: -O-, -NH-, -S-, , C1 to C 20 Alkylene, wherein Indicates the connection point between the group and the rest of the molecule; - Each R5 and R7 independently represents H, halogen, cyano, or C1 to C2. 20 Alkyl, C1 to C 20 Alkyl groups are optionally halogenated, cyanoized, or C1 to C2 at one or more positions. 12 Alkyl, C1 to C 12 Alkoxy substitution, and / or one or more carbon atoms are substituted with one or more heteroatoms selected from O, N, and S; - The molar mass of R6 is 100 to 2000 g / mol; (3) A stabilizer composition, wherein the stabilizer composition comprises an organic acid and a polymerization inhibitor; and (4) Photoinitiator.

2. The composition of claim 1, wherein the composition has one or more of the following characteristics: (1) R1 and R4 have branched structures; Preferably, R1 and R4 have the following structure ， a, b, and c are each independently selected from integers from 0 to 10, provided that a + b + c is less than or equal to 20. (2) Wherein R2 and R3 have a linear structure; preferably R2 and R3 are selected from: methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 1,13-tridecylene, 1,14-tetradecylene, 1,14-pentadecanylene, 1,15-hexadecylene, 1,16-heptadecylene, 1,17-octadecylene, 1,18-nonadecanylene, 1,19-eicosylene; (3) where n and m represent integers from 1 to 20 independently; (4) The molecular weight of the terminal thiol compound is 1,000 to 10,000, or 2,000 to 5,000; (5) The mass fraction of the terminal thiol compound is from 50% to 75% by weight, relative to the total weight of the composition; (6) Each of R5 and R7 independently represents H, methyl, or ethyl; (7) The terminal double bond compound is selected from: , ,or ; (8) Wherein R6 is a residue formed by removing the terminal hydroxyl group from a polyether diol; preferably R6 is a residue formed by removing the terminal hydroxyl group from polyethylene glycol or polypropylene glycol, and the degree of polymerization of the polyethylene glycol or polypropylene glycol is 2 to 100. (9) The molecular weight of the terminal double bond compound is 200 to 10,000, or 200 to 2,000; (10) The mass fraction of the terminal double bond compound is from 15% to 30% by weight, relative to the total weight of the composition; (11) The organic acid is selected from one or more of the following: (meth)acrylic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, lactic acid, benzoic acid, phenylacetic acid, salicylic acid, methylbenzoic acid, tert-butylbenzoic acid, and naphthoic acid; (12) The polymerization inhibitor is selected from one or more of the following: - Phenolic polymerization inhibitors, such as hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-p-cresol (BHT), tert-butylhydroquinone (TBHQ), and p-tert-butylcatechol (TBC). - Quinone polymerization inhibitors, such as p-benzoquinone, tetrachlorobenzoquinone, and 1,4-naphthoquinone; - Amine polymerization inhibitors, such as N,N'-di-sec-butyl-p-phenylenediamine (DBPPD), phenothiazine (PTZ), and triethylamine; - Inorganic salts, such as copper sulfate, ferrous sulfate, and sodium nitrosoferricyanide; (13) The mass fraction of the stabilizer composition is from 0.4% to 1.0% by weight, relative to the total weight of the composition; (14) In the stabilizer composition, the mass ratio of organic acid to polymerization inhibitor is 0.8:1 to 2:1, or 1:1 to 1.5:1; (15) The photoinitiator is selected from one or more of the following: - Benzoin derivatives, such as benzoin, dimethyl benzoate, ethyl benzoate, isopropyl benzoate, and butyl benzoate; - Benzophenones, such as benzophenone, 4-methylbenzophenone, 2-hydroxybenzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(diethylamino)benzophenone; (16) The composition of claim 1, wherein the photoinitiator is present in a mass fraction of 0.5% to 0.85% by weight relative to the total weight of the composition.

3. The composition as claimed in any of the preceding claims, wherein the composition further comprises one or more of the following: a photoalkali-generating agent, a thickener, a plasticizer, and a filler; Preferably, the composition has one or more of the following characteristics: (1) The photoalkali-producing agent is selected from quaternary ammonium salt photoalkali-producing agents, such as TBD·HBPh4, tetrabutylammonium phenylacetate, benzyltrimethylammonium phenyl glycolate, tetramethylammonium naphthate, o-nitrobenzyltrimethylammonium chloride, o-nitrobenzyltrimethylammonium bromide, and bis-o-nitrobenzyldimethylammonium hexafluorophosphate. (2) The mass fraction of the photoalkali-producing agent is 0.3% to 1% by weight, relative to the total weight of the composition; (3) The tackifier comprises acrylate silane coupling agents and mercapto silane coupling agents, wherein the acrylate silane coupling agent has the following structure: The mercapto-based silane coupling agent has the following structure: Where R8 is -H or -CH3, R9 and R 10 Each can be independently -CH3 or -CH2CH3. x and y are each independently between 1 and 3. Groups d and e can be independently scored from 1 to 5. The molar ratio of the acrylate silane coupling agent to the mercapto silane coupling agent is from 1:0.5 to 1:1.5; (4) The mass fraction of the tackifier is 1.0% to 1.5% by weight, relative to the total weight of the composition; (5) The plasticizer is selected from one or more of the following: butyl benzyl phthalate, dibutyl phthalate, or chlorinated paraffin; (6) The plasticizer has a mass fraction of 1% to 5% by weight, relative to the total weight of the composition; (7) The filler is selected from fumed silica; (8) The mass fraction of the filler is from 1% to 15% by weight, relative to the total weight of the composition.

4. The composition as claimed in any of the preceding claims, wherein the viscosity of the composition increases by less than 10% during a 6-month storage period.

5. An article thereof, which is obtained by curing the composition as described in claim 1.

6. The article of claim 5, wherein the article has one or more of the following features: (1) The tensile strength of the product is greater than 1 MPa; (2) The elongation at break of the product is greater than 100% or greater than 150%; (3) After aging for 1000 hours, the tensile strength retention rate of the product is greater than 80%, and the aging is carried out by spraying 5% NaCl solution at 35°C; (4) After aging for 1000 hours, the product retains more than 80% of its elongation at break, and the aging is carried out by spraying a 5% NaCl solution at 35°C. (5) After the product is soaked in No. 3 kerosene at 60°C for 7 days, the weight change rate is less than 5%.

7. Use of the composition as described in claim 1 in the preparation of a sealant.

8. The use as described in claim 7, wherein the composition is at a wavelength of 365 nm and an intensity of 80 mW / cm. 2 Under ultraviolet light, it is completely cured within 60 seconds.

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